Danny Grainger's 30-yard strike secured Hearts' first league win at Tynecastle since the opening day of the season.
The former St Johnstone left-back was given time and space to fire past Darren Randolph in the Motherwell goal.
Both sides felt they should have had penalties, but referee Willie Collum was unmoved by the claims.
Well's Nicky Law had a header cleared off the line as Hearts' win moved them up to eighth and Well stay sixth after their first away league defeat.
Motherwell knew that a win would move them in to third place in the Scottish Premier League and they made a bright start, goalkeeper Jamie MacDonald touching Jamie Murphy's 20-yard shot wide.
Danny Grainger fires an unstoppable drive towards the Motherwell goal
Hearts' Arvydus Novikovas was proving dangerous and, as he collected Andy Driver's pass and drove into the box, the Lithuanian appeared to be caught by Shaun Hutchison but elected to stay on his feet and his touch took him away from goal and the chance was gone.
The home team continued to have the upper hand and Englishman Driver was next to try his luck, his curling effort going just wide from the edge of the box.
Hearts had not lost three consecutive matches at Tynecastle since December 2007 and were not to be denied, going ahead within 15 minutes.
A quickly taken free-kick allowed left-back Grainger to advance from just inside the Motherwell half and he unleashed a left-footed thunderbolt to leave goalkeeper Randolph with no chance.
The hosts were dominant and Ryan Stevenson's header was deflected wide from a Grainger cross.
Stuart McCall's side finally managed an effort on target after almost 25 minutes. Hearts were claiming handball as Michael Higdon laid the ball back to Murphy, whose effort was comfortably saved by Hearts goalkeeper MacDonald.
It was the visitors who were enjoying the bulk of the possession now, but they were also struggling to create any clear openings and Keith Lasley and Humphrey both fired wide.
Motherwell felt they should have had a penalty when Andy Webster bundled Higdon over in the box. Referee Collum decided the Hearts' defender won the header cleanly.
The same pair were involved shortly after at the opposite end, Webster evaded Higdon, but he could not make a proper connection and failed to trouble Randolph.
Higdon nearly drew his side level early in the second half after being found by Humphrey, but his shot flashed just wide of the target.
The second 45 lacked the same fluency as the first, but Ryan Stevenson was next to go close, his drive from 30 yards going a whisker wide of the junction of the post and the bar.
Grainger nearly gifted Well an equaliser when he was robbed by Humphrey, who fed Higdon - the former St Mirren striker's effort was straight at MacDonald in the Hearts goal.
Substitute John Sutton should have put John McGlynn's team two goals ahead after 68 minutes, but his header dropped inches wide of the post.
Motherwell thought they were level with around 15 minutes to play, but Webster was on hand to clear Law's header off the line.
Full Time The referee signals the end of the game.
Free kick awarded for an unfair challenge on Scott Robinson by Stewart Carswell. Direct free kick taken by Ryan Stevenson.
Outswinging corner taken from the right by-line by Chris Humphrey.
Substitution Mehdi Taouil leaves the field to be replaced by Dylan McGowan.
Substitution (Hearts) makes a substitution, with Dylan McGowan coming on for Mehdi Taouil.
Mehdi Taouil produces a right-footed shot from deep inside the penalty area which goes wide of the right-hand post.
Foul by Scott Robinson on Omar Daley, free kick awarded. Direct free kick taken by Fraser Kerr.
Unfair challenge on Marius Zaliukas by Michael Higdon results in a free kick. Free kick taken by Jamie MacDonald.
Simon Ramsden concedes a free kick for a foul on John Sutton. Free kick taken by Daniel Grainger, The ball is crossed by Stevie Hammell.
Substitution Omar Daley on for Nicky Law.
Shot from deep inside the area by Scott Robinson goes over the bar.
Effort from inside the area by Callum Paterson misses to the right of the target.
Simon Ramsden takes the direct free kick.
Booking Mehdi Taouil booked.
Free kick awarded for a foul by Simon Ramsden on John Sutton. Scott Robinson restarts play with the free kick. Mehdi Taouil handles the ball and concedes a free kick.
Tom Hateley delivers the ball from the free kick right-footed from own half, Andy Webster manages to make a clearance. Corner from left by-line taken by Tom Hateley.
Booking Scott Robinson is shown a yellow card for unsporting behaviour.
Henrik Ojamaa takes a shot. Clearance made by Andy Webster. Free kick awarded for an unfair challenge on Nicky Law by Scott Robinson.
Substitution Henrik Ojamaa is brought on as a substitute for Jamie Murphy.
Unfair challenge on Callum Paterson by Stevie Hammell results in a free kick. Free kick taken by Scott Robinson.
Michael Higdon gives away a free kick for an unfair challenge on Andy Webster. Jamie MacDonald takes the direct free kick.
Substitution Scott Robinson is brought on as a substitute for Darren Barr.
Free kick awarded for an unfair challenge on Daniel Grainger by Chris Humphrey. Free kick taken by Jamie MacDonald.
Corner from the left by-line taken by Daniel Grainger, clearance by Fraser Kerr. John Sutton has a headed effort at goal from deep inside the area missing to the right of the target.
Substitution John Sutton on for Arvydas Novikovas.
Keith Lasley takes the free kick.
Booking Marius Zaliukas is given a yellow card.
Marius Zaliukas concedes a free kick for a foul on Keith Lasley.
Michael Higdon takes a shot. Jamie MacDonald makes a comfortable save.
Ryan Stevenson has shot on goal from just outside the area which goes wide of the right-hand upright.
Ryan Stevenson has an effort at goal from deep inside the area missing to the right of the target.
Mehdi Taouil concedes a free kick for a foul on Jamie Murphy. Keith Lasley restarts play with the free kick.
Outswinging corner taken by Ryan Stevenson from the right by-line, Headed effort from deep inside the area by Darren Barr misses to the right of the target.
Effort on goal by Michael Higdon from deep inside the penalty area misses to the right of the target.
Chris Humphrey gives away a free kick for an unfair challenge on Daniel Grainger. Daniel Grainger takes the free kick.
The second half begins.
Substitution Stewart Carswell comes on in place of Shaun Hutchinson.
45:00 +0:58 Half time
Half Time The ref blows to end the first period.
Darren Barr has an effort at goal from just outside the box which goes wide of the right-hand post.
Corner from right by-line taken by Tom Hateley.
Corner taken right-footed by Tom Hateley from the right by-line, Andrew Driver makes a clearance.
Corner from the right by-line taken by Tom Hateley, Marius Zaliukas manages to make a clearance.
Free kick awarded for a foul by Darren Barr on Tom Hateley. Tom Hateley restarts play with the free kick.
The referee blows for offside against Callum Paterson. Darren Randolph takes the free kick.
Unfair challenge on Ryan Stevenson by Simon Ramsden results in a free kick. The free kick is swung in left-footed by Daniel Grainger, Tom Hateley manages to make a clearance.
Strike on goal comes in from Tom Hateley from the free kick, Daniel Grainger gets a block in.
Booking Andrew Driver receives a caution.
Unfair challenge on Nicky Law by Andrew Driver results in a free kick.
Outswinging corner taken by Tom Hateley from the right by-line, Daniel Grainger makes a clearance.
Chris Humphrey has an effort at goal from just outside the box which goes wide of the right-hand upright.
Callum Paterson takes a shot. Darren Randolph makes a comfortable save.
Jamie Murphy takes a shot. Save made by Jamie MacDonald.
Shot by Keith Lasley from deep inside the penalty area misses to the right of the goal.
Keith Lasley has an effort at goal from deep inside the area missing to the right of the target.
Corner taken by Daniel Grainger, Ryan McGowan takes a shot. Save by Darren Randolph.
13:54 Goal scored
Goal - Daniel Grainger - Hearts 1 - 0 Motherwell Daniel Grainger grabs a goal from outside the penalty box to the top right corner of the goal. Hearts 1-0 Motherwell.
Headed effort from inside the box by Ryan Stevenson misses to the right of the target.
Assist by Ryan Stevenson.
13:54 Goal scored
Goal - Daniel Grainger - Hearts 1 - 0 Motherwell Daniel Grainger gets on the score sheet with a goal from outside the penalty area to the top right corner of the goal. Hearts 1-0 Motherwell.
Free kick awarded for a foul by Michael Higdon on Mehdi Taouil. Ryan Stevenson takes the free kick.
Foul by Jamie Murphy on Darren Barr, free kick awarded. The free kick is swung in left-footed by Daniel Grainger.
Stevie Hammell concedes a free kick for a foul on Mehdi Taouil. Andy Webster takes the direct free kick.
Andrew Driver produces a right-footed shot from just outside the box that misses to the right of the goal.
The referee blows for offside. Indirect free kick taken by Stevie Hammell.
Foul by Ryan Stevenson on Tom Hateley, free kick awarded. Free kick taken by Stevie Hammell. Unfair challenge on Marius Zaliukas by Michael Higdon results in a free kick. Jamie MacDonald takes the free kick.
Jamie Murphy takes a shot. Corner taken right-footed by Tom Hateley, save by Jamie MacDonald. Save made by Jamie MacDonald.
The ref blows the whistle to start the match.
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