Two first-half goals from Billy McKay, who later spurned a chance to claim his hat-trick when he missed from the penalty spot, were sufficient enough to overcome a Hearts side that finished with 10 men when Jamie Hamill saw red.
For the fifth game in succession, Caley Thistle named an unchanged starting line-up as they looked to maintain their unbeaten start to the season.
Hearts made the trip to the Highlands without the suspended defensive duo of Danny Wilson and Kevin McHattie.
Jamie MacDonald, however, had recovered from an ankle injury he sustained in the Scottish League Cup victory on penalties over Raith Rovers and took his place in goal.
David Smith, Callum Tapping and Jordan McGhee also came into the side, while Billy King dropped down to the substitutes bench.
Hearts, who had only beaten Caley Thistle once in their nine previous meetings, were first to threaten, but Jamie Walker skewed his shot from 14 yards wide of goal.
Inverness had not lost to the Jambos in the Highland Capital for three years and that record looked set to continue after just nine minutes.
David Raven sent Aaron Doran away down the right and he had time to look up, picking out the unmarked McKay, who from 10 yards out produced a controlled shot that was helped into the roof of the net by MacDonald.
The visitors almost responded as good work by Callum Paterson set up Walker, but from a tight angle he rolled a shot across goal and narrowly wide.
After Nick Ross had dragged his 25-yard drive past the post, Caley Thistle doubled their advantage in the 32nd minute courtesy of a swift counter attack.
McKay controlled Ross Draper's clearance and headed towards the Hearts goal before finding Doran. His shot was blocked, but it flew across goal to where McKay was lurking at the back post and from six yards he made no mistake.
Hearts needed something to galvanise them and they were almost gifted an equaliser as the interval approached.
Graeme Shinnie lost possession allowing Walker to burst through on goal. He beat home goalkeeper Dean Brill from 14 yards, but his thumping drive rebounded to safety via the upright.
At the other end, Doran opted to try his luck 20 yards from goal, yet his low shot lacked the power to seriously trouble MacDonald.
Inverness set about trying to end the game as a contest early in the second half and Gary Warren saw his header come back off the bar.
McKay retrieved the loose ball and promptly set up the onrushing Vincent, but from close range he sent his shot well a yard wide.
Ross then did well on the left to produce a low cross that McKay poked wide, before the latter fired straight at MacDonald when well placed 14 yards out.
Not long after, MacDonald had to produce real heroics to keep out Richie Foran's strike from distance as Caley Thistle continued to apply the pressure.
The Hearts goalkeeper could have done nothing, however, when Doran latched on to Raven's throw-in, but his fizzing volley dipped just over.
A mistake by Scott Robinson then allowed McKay a clean run through on goal, yet he took too long to make up his mind, eventually being forced wide by MacDonald and the opportunity was gone.
Inverness were then presented with a wonderful chance in the final stages when they were given what seemed a harsh penalty.
After MacDonald had superbly denied Foran, McKay's attempts to turn home the rebound were blocked by Hamill.
Referee John Beaton, however, surprised everyone by pointing to the spot before sending the Hearts captain off for what the match official deemed to be a handball.
McKay took responsibility for the penalty in a bid to claim the match ball, but his low effort was saved down to his right by the excellent MacDonald.