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Indeed, it was Burnley who started the stronger, with Wade Elliott giving Blues skipper Wayne Bridge trouble all game down Burnley's right flank.
The first clear cut chance fell to the hosts, with the fit-again Didier Drogba laying a superb through ball into the path of Salomon Kalou. Kalou tried to round 'keeper Brian Jensen but the big Dane thrust out a leg to deny him, and then saved Florent Malouda's follow-up. Jensen would also soon deny Drogba by beating away his firm hit.
Chelsea were content to push the ball around in their own half, and Burnley were happy to restrict them to efforts from range.
However, the introduction of Frank Lampard, on for Juliano Belletti who hobbled off, threatened to take the game away from Burnley. Lampard had been on the field just moments when he found Drogba just outside the corner of the penalty area. The Ivorian beat the otherwise colossal Michael Duff too easily in the Burnley defence, before waltzing past Clarets captain Steven Caldwell and bending an unstoppable shot into the corner.
Drogba celebrated stupidly in front of the visiting hordes, and was pelted with coins and objects by a moronic few. Drogba picked one of the coins up and hurled it back, and despite his speed to apologise post-match, he will almost certainly face an FA charge for his actions.
Burnley, backed by over 6000 voracious fans, took the hit to the chin well though, and grew into the match from there. But it could have been two-nil just before the break, when Chelsea defender Ivanovic turned a cross on to the bar.
Burnley had only sniffs at goal in the first period, with Cudicini denying Chris Eagles and Martin Paterson. But after the break it was a different story. Owen Coyle instilled calm into the Burnley midfield and from there the Clarets took the game to their illustrious opponents.
Joey Gudjonsson was a driving force, and when Chelsea boss Scolari took off Deco and Drogba, his influence grew further. In hindsight, it seemed a rash decision from the former Portuguese head coach with half an hour remaining of the game and his side holding only a slender lead.
Burnley manager Owen Coyle turned to veteran Ade Akinbiyi, and the infamous Premiership flop came up trumps less than ten minutes after entering the game. Eagles attacked strongly down the flank and cut in dangerously, forcing Cudicini to turn his shot back into the goalmouth. The ball took an age to reach Akinbiyi, who kept the coolest head in West London to force home an improbable equaliser, sending the Shed End into ecstasy.
It was another managerial masterstroke from Coyle, who sent on youngster Jay Rodriguez to score the winner against Fulham in the previous round.
Most of the travelling fans would have been delighted with just a consolation goal, but suddenly Burnley, driven on by terrific support, sensed the most unlikely of victories, and pressed on.
Chelsea could have won it at the death after forcing numerous corners, with both Alex and substitute striker Franco di Santo, who would later limp off leaving the Blues down to ten men, guilty of poor misses.
But Burnley held on, and saw out a fascinatingly poised yet mostly uneventful thirty minutes of extra time to take the tie to penalty kicks, but not before Caldwell saw red after a second booking for a clumsy challenge with just moments to play.
With Chelsea's recent record in penalties, Burnley must have sensed their chance, despatching their first four kicks safely with the minimum of fuss. Bridge had Chelsea's second well saved by Jensen, who then proved to be the hero for the visitors.
Elliott missed his chance to win it for Burnley, but after Duff scored the opening kick of sudden death, Jensen spectacularly turned Mikel's shot onto the post, sending Chelsea out of the competition and thousands of Lancastrians beyond delight.
Burnley celebrated the victory at length, with the players and coaching staff all making their way to the front of the Shed End to show their appreciation for such fantastic away support.
Owen Coyle has his team playing football in the right manner, collecting great results along the way. The Clarets will be the team to avoid for the remaining big boys of Arsenal, United and Spurs after this headline-grabbing win.