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.
Nicholson (far right) netted his first Killie goal
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.
Highlights - Kilmarnock 1-2 Hibernian
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.
Live text and stats
Saturday, 24 August 2013
26 O'Hara yellow card
04 Fowler (Johnston 89)
14 Heffernan (Gross 77)
19 Handling yellow card
20 Taiwo (Horribine 90)
09 Vine yellow card (Stanton 84)
14 Collins (Caldwell 77)
Ref: ClancyAtt: 3,807
Attempts on target
Attempts off target
90:00+4:10 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 Dean Horribine is brought on as a substitute for Tom Taiwo.
88:11 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 Sam Stanton replaces Rowan Vine.
Correction - 79:39 Assist on the goal came from Lewis Stevenson.
79:39 The assist for the goal came from Owain Tudur Jones.
79:39 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 Paul Heffernan goes off and William Gros comes on.
76:06 Substitution (Hibernian) makes a substitution, with Ross Caldwell coming on for James Collins.
75:42 Free kick taken by Ben Williams.
75:14 Booking for Danny Handling for dissent.
75:06 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.
50:34 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.
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