First-half goals from skipper Ian Murray and Tom McManus gave Hibs their first home win of the season and lifted the Easter Road side off the bottom of the table.
Spanish ace Paco Luna was the creator for both strikes which came in a three-minute spell to leave Killie reeling.
And the win, only the second of the season, will be all the more sweet for under pressure Hibs boss Bobby Williamson as it came against his former side.
The first came on eight minutes when Gary Smith delivered a free-kick deep in the Killie area, Luna outjumped the visiting defence headed back across goal where skipper Murray was unmarked to hook the ball past Gordon Marshall.
Three minutes later Hibs added a second with Luna again the creator. His throughball left the Killie backline flat-footed and McManus slipped the ball under the advancing Marshall for a goal the veteran keeper will want to forget.
Luna continued to torment the visitors but was a bit ambitious with a left-foot effort from fully 25 yards after 16 minutes.
Steve Fulton did his best to drive Kilmarnock forward but when he did he found a Hibs backline superbly marshalled by Yannick Zambernardi which, while not always pretty, proved effective in breaking up the few attacks Killie could muster.
McManus and Grant Brebner managed to get in each others way when either one of them could probably have sent Janos Matyus' 35th minute cross goalwards.
Killie's best effort of the first half came on the half hour mark but, with the Hibs defence for once out of position, neither Jose Quitongo or Kris Boyd could get a touch on Peter Canero's low cross.
If Luna had been the star of the first half then keeper Nick Colgan was equally impressive after the break.
Fully justifying his recall to the side he produced a stunning double save after 49 minutes to deny first Alan Mahood and then Barry McLaughlin when the defender was first to react to the rebound.
McManus could have had a second after 55 minutes but his shot on the turn from the edge of the area was just wide while substitute Gary O'Connor was well off target with an ambitious effort eight minutes later.
Kilmarnock finally came to life late in the game but a spell of concerted pressure could produce only a weak effort from Freddy Dindeleux and a Canero strike seven minutes from time which Colgan did well to block at point-blank range