Adam Rooney's second half hat-trick, taking his goal tally for the season to 13 in all competitions, added to Richie Foran's seventh-minute opener as Caley Thistle claimed just their second home league win of the campaign.
Inverness had their cause aided, however, by a red card being shown to Paul Hanlon just five minutes after coming on as a substitute at the start of the second half.
Derek Riordan and a Liam Miller penalty twice threatened to give Hibs a way back into the match, but they were ultimately undone by Rooney's clinical finishing, which included a spot-kick.
Caley Thistle made two changes from the side that won 3-1 at Hamilton Accies last time out.
Under the terms of his loan agreement, Hibernian defender Kevin McCann could not feature, while young midfielder Gavin Morrison dropped to the bench. In came Lee Cox, now fully recovered from an ankle injury, while Russell Duncan returned following a groin problem to anchor the midfield.
Following consecutive SPL victories over Rangers and Motherwell, Hibs manager Colin Calderwood made one alteration with Colin Nish, back after an ankle knock, replacing Lithuanian forward Valdas Trakys.
There had barely been a chance worthy of the name when Caley Thistle forged in front with only seven minutes gone.
Foran worked a neat one-two with fellow Irishman Rooney and striding on to the return pass he dispatched a low shot past the outstretched arm of former Inverness goalkeeper Mark Brown from just inside the box for his first goal of the season.
A Hibs response was slow in coming, although John Rankin, another ex-Caley Thistle player in the visitors line-up, fired in a low shot that bounced a yard wide of the post having been set up by Colin Nish.
Some sloppy defending by the home side then led to Hibs creating a couple of chances with Ryan Esson having to tip Miller's deep cross on to his own crossbar and away to safety, before Edwin De Graaf sent a close range effort wide from eight yards.
Hibs, however, had nothing to show for their flurry of chances and only a wonderful reaction save by Brown prevented Nick Ross from scoring with a header after Foran's miss-hit shot hand bounced kindly into his path.
If Brown's stop from youngster Ross was good then his second save from Rooney moments later was even better.
From a swift counter attack, Jonny Hayes excellent cross picked out Rooney who stooped low to get in an effort that Brown somehow managed to touch on to the crossbar before the loose ball bounced away to safety.
Hibs were struggling to cope with crosses into their box and Foran may feel he should have done better than skew an effort into the side netting when he stole in unmarked ay the back post to get on the end of another Hayes delivery.
In a bid to change his sides fortunes going into the second half, Calderwood sent on Daniel Galbraith and Hanlon for De Graaf and Michael Hart respectively. It was a move, however, that backfired just six minutes after the restart.
Duncan's inswinging corner caused chaos in the visitors' defence and Rooney seemed certain to dispatch the loose ball until Hanlon stopped the ball on the line with his hand.
Referee Steve Conroy was left with no option but show Hanlon the red card and further misery was heaped on Hibs when Rooney sent the penalty in to corner, despite Brown guessing the right way.
Rooney then had a chance to add to his tally, when he collected Duncan's cross, but his volley on the turn comfortably cleared the bar.
Hibs had been on the backfoot but they were gifted a way back into the game in the 66th minute. Hayes' attempted backpass was woefully short and Riordan was quick to seize on it, taking it past the onrushing Esson before slotting it into the empty net.
Hopes of a Hibs comeback, however, lasted four minutes as Hayes went some way to atoning for his error.
Breaking quickly, the winger surged forward before delicately chipping the ball into the path of Rooney, who kept his composure to fire a low shot beyond the exposed Brown.
But still Hibs were not finished and once more Caley Thistle were the architects of their own downfall.
Ross Tokely felled Nish inside the area, from which he was booked, and from the spot Miller remained calm to chip the ball home from 12 yards in the 78th minute.
The response by the home side yet again, however, was decisive as they restored their two-goal lead barely two minutes later.
Hayes was again the provider, slipping the ball into the path of Rooney who once more finished with conviction to complete his hat-trick.
It was to prove the final goal of an eventful match as Caley Thistle did just about enough to merit the triumph.