A Liam Craig double secured Hibernian's first win of the season to ease some of the pressure on under-fire manager Pat Fenlon.
The Easter Road side came from behind to leave Allan Johnston still looking for his first victory as Kilmarnock boss.
Barry Nicholson's first Killie goal gave the hosts a first-half lead.
But Craig headed Hibs level before firing the winner as the match entered its closing stages.
And a vote of confidence for Fenlon and his players from chairman Rod Petrie in midweek seems to have paid dividends with a win in Ayrshire.
The visitors thought they had taken the lead early on when Rowan Vine had the ball in the net following a sweeping move involving James Collins and Owain Tudur Jones.
Vine swept home but the former St Johnstone striker was flagged offside.
Recent signing Nicholson then celebrated his birthday in spectacular style. On the day he turned 35, the midfielder showed terrific technique blasting a volley from a similar number of yards to his years into the top left-hand corner.
Killie came close to adding a second when Paul Heffernan flicked a Sean Clohessy cross over from close range.
Hibs were unbeaten in their five fixtures against Killie last season and expected that trend to continue when they equalised within two minutes of the second half getting underway.
Vine found space on the right to send over a perfect cross for Craig to head down beyond Craig Samson.
Kilmarnock pushed forward to try and restore their lead and Mark Stewart's shot was turned around the post by Ben Williams.
From the resulting corner the hosts went close again. Nicholson's delivery from the right was laid into the path of Darren Barr by Jackson Irvine and the big defender's curling effort flew just wide.
Samson had to be alert to make two saves within the space of two minutes. First, he dived low to his right to turn away a Jones strike before clutching a header on the line from former Killie defender Michael Nelson.
But Hibs did take took the lead when Craig netted his second of the afternoon.
It looked as though Barr was favourite to deal with a bouncing ball but he delayed and allowed Craig to nip it off his toe and send a lob over the advancing Samson into the empty net.
Killie should have equalised in the final minute of stoppage time when substitute Chris Johnston blasted over from 10 yards when it had looked easier to score.
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Live Text Commentary
Full Time The referee brings the game to a close.90:00 +2:58
Shot by Chris Johnston missed to the left of goal.90:00 +2:41
Barry Nicholson restarts play with the free kick.90:00 +2:31
Free kick awarded for an unfair challenge on Mark O'Hara by Owain Tudur Jones.89:12 Substitution
Substitution Dean Horribine is brought on as a substitute for Tom Taiwo.88:11 Substitution
Substitution Chris Johnston on for James Fowler.87:24
Short corner taken by Sam Stanton from the right by-line.85:48
William Gros takes a shot and went wide of the left-hand post.83:54 Substitution
Substitution Sam Stanton replaces Rowan Vine.79:39
Assist on the goal came from Lewis Stevenson.79:39 Goal scored
Goal! - Liam Craig - Kilmarnock 1 - 2 Hibernian Liam Craig scores with a right foot finish. Kilmarnock 1-2 Hibernian.78:55
Free kick taken by Jackson Irvine.78:45
Rowan Vine is penalised for handball and concedes a free kick.78:29
Free kick taken by Craig Samson.78:05
The assistant referee signals for offside against Rowan Vine.76:37 Substitution
Substitution Paul Heffernan goes off and William Gros comes on.76:06 Substitution
Substitution (Hibernian) makes a substitution, with Ross Caldwell coming on for James Collins.75:42
Free kick taken by Ben Williams.75:14 Booking
Booking for Danny Handling for dissent.
The referee shows Mark O'Hara a yellow card.74:42
Foul by Mark O'Hara on Owain Tudur Jones, free kick awarded.74:09
Owain Tudur Jones heads at goal. Craig Samson safely holds on.74:01
Corner taken by Liam Craig from the left by-line.73:32
Owain Tudur Jones takes the chance to get an effort at goal.71:00
Clearance made by Jackson Irvine.70:56
Liam Craig restarts play with the free kick.69:36
Free kick awarded for an unfair challenge on James Collins by James Fowler.68:05
James Fowler has an effort at goal. Ben Williams catches the ball.65:00
Darren Barr takes the chance to get an effort at goal and missed to the left of the net.64:52
Corner from the right by-line taken by Barry Nicholson.64:25
Mark Stewart takes a shot. Ben Williams turns it away with a finger tip save.63:51
Craig Samson restarts play with the free kick.63:31
Free kick awarded for an unfair challenge on James Fowler by Tom Taiwo.62:10
Michael Nelson manages to make a clearance.62:06
The ball is swung over by Rabiu Ibrahim.60:22
Owain Tudur Jones manages to make a clearance.60:14
A cross is delivered by Sean Clohessy.58:59
Rabiu Ibrahim has an effort at goal and missed to the left of the goal.58:49
A cross is delivered by Sean Clohessy.58:15
Clearance by Paul Hanlon.58:09
Barry Nicholson delivers the ball.57:13
Centre by Lewis Stevenson.56:49
Ben Williams takes the free kick.56:37
The referee blows for offside against Mark Stewart.52:01
Clearance made by Michael Nelson.51:59
Corner from the right by-line taken by Barry Nicholson.51:14
Craig Samson restarts play with the free kick.50:44
Booking for Rowan Vine for unsporting behaviour.50:44 Booking
Free kick awarded for a foul by Rowan Vine on Sean Clohessy.49:51
Ben Williams restarts play with the free kick.49:36
Jeroen Tesselaar challenges Rowan Vine unfairly and gives away a free kick.49:06
Clearance by Michael Nelson.48:59
Corner taken by Barry Nicholson.46:25
Assist by Rowan Vine.46:25 Goal scored
Goal! - Liam Craig - Kilmarnock 1 - 1 Hibernian Liam Craig scores. Kilmarnock 1-1 Hibernian.46:20
Rowan Vine sends in a cross.45:01
The second half begins.45:00 +0:08 Half time
Half Time The ref blows to end the first period.43:16
Jackson Irvine manages to make a clearance.43:11
Liam Craig restarts play with the free kick.42:40
Rowan Vine fouled by Darren Barr, the ref awards a free kick.40:02
Ben Williams restarts play with the free kick.39:42
The offside flag is raised against Sean Clohessy.39:13
The ball is crossed by Barry Nicholson.36:01
Darren Barr manages to make a clearance.35:56
Liam Craig restarts play with the free kick.35:40
Foul by Jackson Irvine on Rowan Vine, free kick awarded.35:14
Free kick taken by Craig Samson.35:01
The assistant referee flags for offside against Rowan Vine.34:28
Danny Handling produces a cross.33:27
Free kick crossed by Barry Nicholson.33:03
Tom Taiwo concedes a free kick for a foul on Barry Nicholson.32:38
Clearance made by Michael Nelson.32:33
Centre by Sean Clohessy.32:09
Mark O'Hara manages to make a clearance.32:04
Liam Craig crosses the ball in from the free kick.31:47
James Fowler challenges James Collins unfairly and gives away a free kick.29:49
Darren Barr restarts play with the free kick.29:30
Owain Tudur Jones challenges Mark O'Hara unfairly and gives away a free kick.29:15
Ben Williams takes the free kick.29:06
Mark Stewart is flagged offside by the assistant referee.22:08
Assist by Paul Heffernan.22:08 Goal scored
Goal! - Barry Nicholson - Kilmarnock 1 - 0 Hibernian Barry Nicholson scores with their right foot. Kilmarnock 1-0 Hibernian.20:55
Darren Barr takes the free kick.20:43
Free kick awarded for an unfair challenge on James Fowler by Tom Taiwo.19:16
Header by Darren Barr misses left.19:06
Corner taken by Barry Nicholson from the right by-line.18:24
Darren Barr crosses the ball in from the free kick.17:56
James Collins is ruled offside.17:44
Corner taken by Liam Craig from the left by-line.15:57
Owain Tudur Jones produces a cross.15:40
Free kick taken by Paul Hanlon.15:27
The referee blows for offside against Paul Heffernan.13:07
Craig Samson takes the free kick.12:43
The official flags Owain Tudur Jones offside.10:25
Free kick taken by Sean Clohessy.9:42
Ryan McGivern gives away a free kick for an unfair challenge on Barry Nicholson.8:53
Michael Nelson manages to make a clearance.8:47
Jeroen Tesselaar delivers the ball.8:27
Corner from the right by-line taken by Barry Nicholson.6:18
Craig Samson takes the free kick.5:50
The referee blows for offside.5:49
The ball is sent over by Owain Tudur Jones.4:11
Corner from the left by-line taken by Barry Nicholson.1:22
Michael Nelson takes the free kick.1:03
Foul by Jeroen Tesselaar on James Collins, free kick awarded.0:00
The match has kicked off.
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