The English team trailing from the first leg had taken a 3-0 lead on the night inside the first 19 minutes through Eidur Gudjohnsen Frank Lampard and Damien Duff only to be rocked back by two away goals from Ronaldinho - one a penalty the other a sublime chip. It remained thrilling end-to-end stuff but Chelsea had the last word.
As expected Gudjohnsen was named as Didier Drogba's replacement in the Chelsea attack and Mateja Kezman was also included with Joe Cole dropping back into a midfield role at the expense of Tiago. Barça welcomed back central defender Oleguer Presas after injury but were without Rafael Márquez. Andrés Iniesta was named in attack instead of Ludovic Giuly.
Barcelona had anticipated a fierce onslaught from the home side in the early stages but instead it was they who dominated possession and were first to work a good position as Juliano Belletti got away.
Chelsea had struggled to get a feel of the ball themselves in the first seven minutes but then a slip by Xavi Hernández gave Lampard the chance to feed Kezman. The ball he played over from the right was exquisite directed right into Gudjohnsen's path and a sidestep was enough to set up the Icelandic striker's decisive finish.
Lampard missed badly before the second goal but made immediate amends as he was on hand to turn home the loose ball after Víctor Valdés had put only one hand on Cole's deflected drive. Incredibly two then became three as Kezman and Cole combined to give Duff a free run through the heart of the defence. Again the finish was assured.
The visitors were badly stung but found encouragement with a Samuel Eto'o drive that Petr Cech clawed away swiftly followed by a Ronaldinho header that missed by centimetres. When Belletti's cross struck the arm of Paulo Ferreira Barça had a route back into the contest. Ronaldinho's penalty was placed just out of Cech's reach.
Eleven minutes later the Brazilian showed just why he is the reigning world player of the year with a sensational outside-of-the-boot shot when nothing looked on for him. It foxed even as good a goalkeeper as Cech who did not even move.
It was a shattering double blow for Chelsea but they continued to look dangerous and Cole was unlucky to strike an upright just before the break. The youngster had made life difficult for Giovanni van Bronckhorst and Frank Rijkaard decided to replace the Dutchman with Sylvinho.
The ebb and flow was no less dramatic; Lampard and Belletti both came close Eto'o unleashed a couple of dynamic runs and when Carles Puyol was left free at a corner it required a magnificent save from Cech. Then as Chelsea took charge again Gudjohnsen was given the chance to put away his volley only to fire the ball against a defender.
Iniesta then had a shot turned on to the post by Cech and that intervention proved crucial as Terry rose to turn in a Duff corner. Barcelona pressed hard in the final minutes hoping for one final twist but it was not to be.