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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