Striker Samuel Eto'o scored the decisive second goal ten minutes from time to kill off 10-man Chelsea who, following the sending off of Asier del Horno took a shock lead only to be pegged back by a John Terry own goal.
In truth, the red card on 36 minutes for Spanish left-back del Horno did little to dispel the fact that Chelsea were outclassed in the midfield area, and it would probably be just to say even with 11 men, Chelsea were clearly second best for long periods of the game.
It took the home side 50 minutes before they had their first shot on target - a less than spectacular Frank Lampard shot which failed to trouble Barcelona's goalkeeper Victor Valdes.
But by then Chelsea were on the back foot after del Horno was sent off for an ungainly challenge on livewire wingman Lionel Messi near the corner flag.
Chelsea had to shuffle their pack, replacing Joe Cole for Geremi in order to restore a four-man defence.
But all the first-half chances fell to the Catalan side with Brazilian Ronaldinho supreme.
He had a 24th minute shot blocked but an even better one six minutes later was brilliantly saved by Petr Cech. But against the run of play the Blues took the lead on 59 minutes.
Lampard, wide on the left had a free-kick and he pelted in a vicious piledriver.
Midfielder Thiago Motta and keeper Valdes got in each other's way and the ball bounced off Motto's leg into the net for an own goal.
Could Chelsea sustain a rearguard defence was the crucial question? Sadly they could not and the lead lasted 12 minutes. Again it was a left sided free-kick which did the damage.
This time Ronaldinho whipped in the ball, but unfortunately for skipper Terry the ball skidded off his head and sailed over the despairing grasp of Cech.
Barcelona, sensing a historic victory, piled forward.
Former Celtic forward Henrik Larsson was sent on to spearhead the attack and he was pivotal to Barcelona's winner.
Again Ronaldinho started the attack, running towards the Chelsea area before sliding the ball wide on the left to Larsson.
The Swedish hit-man passed to Rafael Marquez who crossed deep to the far post and Eto'o, exploiting a vast gap in the left-back area darted in and planted a powerful header into the Chelsea net.