Barcelona were always in control having established a 2-1 lead from the first-leg at Stamford Bridge and on home soil, it was the mesmeric Ronaldinho that ultimately decided the outcome with a fine effort in the 78th minute.
Chelsea were generously awarded a penalty in injury time, which Frank Lampard finished with aplomb but when all the talking ceased, it was Barcelona that proved they have the edge over their Premiership counterparts.
Pre-match and the Camp Nou clash had taken on a mantle that transcended the normal boundaries of sport.
Mourinho pitted against Frank Rijkaard was just the subtext as the game became a battle of aesthetics versus efficiency, of the ruthless over the flamboyant; all played out against a backdrop of Uefa probes and warnings, cat-calling and the type of histrionics normally best kept to the set of a soap opera.
The game did not disappoint but neither did it sparkle, with the exception of Ronaldinho, as the hype had suggested it might.
Mourinho's decision to employ a troika of attacking talent in support of lone front man Didier Drogba saw Chelsea match their Catalan hosts in terms of intent as Joe Cole, Damien Duff and Arjen Robben were all given licence to roam.
The early sparring saw a surprisingly open affair ensue as great slabs of field were left free to run into as Barcelona soon settled in to a bewitching rhythm.
Chelsea too were not without their moments but the first opportunity of note saw Petr Cech called into a comfortable save from Thiago Motta's daisy-cutter before Ronaldinho burst from the shadows to introduce his presence with a step-over which left Paulo Ferreira bewitched.
It was the genius of the Brazilian that conjured the first real consternation for Chelsea as his sumptuous little flick played in Lionel Messi but the Argentine's drive was blocked by Ricardo Carvalho, who was then needed to be at his best again to thwart another rapid Barca break.
Drogba pulled off the shackles of Oleguer to get in a header on the home side's goal from Robben's free kick but Victor Valdes gathered easily before Chelsea's tormentor-in-chief from the first-leg, Messi, came out of an innocuous challenge holding his hamstring and the night was denied one of its chief protagonists.
Messi was substituted in the 23rd minute and the remainder of the half became at times a one-man virtuoso show from Ronaldinho, who looked like he could have been playing beach football with friends such was his enjoyment and complete control of proceedings when in possession.
With the ball becoming a commodity Chelsea saw little of, Barca were dominant but the killer pass eluded the home side as Oleguer wasted a decent opening with a tepid poke at Cech.
On a rare foray Duff struck a half volley wide before Robben cut inside onto his left foot and from the angle brought a save from Valdes.
Set-pieces were always likely to expose the one chink in Barca's armoury and as the half drew to its close, one such dead-ball saw John Terry flick on to Cole, who stretched a leg and lobbed the ball onto the top of Valdes' goal.
Aware that two goals would be required to have any chance of progression Chelsea started on the front-foot after the interval but with Lampard restricted in a holding role, Mourinho's side were too easily contained.
At the other end, an advanced Rafael Marquez forced Terry into an archetypal block to repel the Mexican's volley from the edge of the area.
Mourinho needed just ten minutes of the second half to come to the conclusion that changes were needed and acting decisively, Eidur Gudjohnsen and Hernan Crespo were introduced at the expense of Duff and Drogba.
It was, though, still Barcelona that looked the likelier as Samuel Eto'o took his chance early and forced Cech into a smart parry with Terry then needing to stretch every sinew to repel another Barca counter.
Just past the hour mark and a trademark Crespo run set him free in the box brilliantly, Cole's cross from the left was equal to it, but the striker's finish at the near post was agonisingly wide and Chelsea's best chance of the night was lost.
Although Chelsea were impressive enough defensively, in truth, Mourinho's men were a side devoid of the creative wit needed to prise open a Barcelona defence that was never unduly worried.
When the goal arrived 12 minutes from time it was no surprise it came from Ronaldinho, nor was it a surprise that it was a creation entirely of his own making; an exquisite blend of power, balance, pace and beauty.
A waltz past Carvalho saw a path to goal emerge and bouncing off the robust shoulder of Terry and maintaining his balance, Ronaldinho then slammed the ball low and beyond Cech to ensure that the best side, in both legs, progressed.
Barcelona still had time to hit the post as Eto'o got behind a tired Chelsea backline before in injury time, an advanced Terry was adjudged to have been 'fouled' in the box - somewhat generously - by a stretching Giovanni van Bronckhorst.
A previously peripheral Lampard stepped up to send Valdes the wrong way with the calmest of penalties but it was to prove the final moment of a game that saw the best side in Europe set the standard for the rest.
Barcelona v Chelsea player ratings
| Barcelona | Team Statistics | Chelsea |
| 1 | Goals | 1 |
| 0 | 1st Half Goals | 0 |
| 4 | Shots on Target | 4 |
| 4 | Shots off Target | 6 |
| 7 | Blocked Shots | 0 |
| 2 | Corners | 0 |
| 20 | Fouls | 31 |
| 0 | Offsides | 5 |
| 2 | Yellow Cards | 1 |
| 0 | Red Cards | 0 |
| 74 | Passing Success | 74.1 |
| 27 | Tackles | 35 |
| 55.6 | Tackles Success | 77.1 |
| 55 | Possession | 45 |
| 65.8 | Territorial Advantage | 34.2 |
The Catalans reportedly see the fleet-footed Peruvian international as a sound replacement for Henrik Larsson who will return to Sweden in the summer. 
The Argentinian is currently on loan to Sevilla from the Catalan giants, and it is thought that if Barca were to co-operate in making that deal permanent, the Southern outfit may be more open to allowing Alves to move in the opposite direction. 
Eto'o tried to leave the pitch in the second half but was persuaded to stay by players and coach Frank Rijkaard. 
Echevarría seated in the theater box next to him and Perrín 
The azulgrana technical secretary, Txiki Begiristain, did not discard the interest of the Barça by the goleador of the Villarreal Diego Forlán, although he indicated that this one is not the moment for speaking of draftees but who there will be to hope to that it concludes the season. Txiki defined to the Uruguayan like "a player who made an extraordinary campaign the year last and that in this one has recovered the goal". On his possible incorporation for the next campaign, in which Larsson will not be after having announced its draftee by the Swedish Helsingborg, it was limited to aim that "it is not moment for speaking from whom can come to the Barça and who no. The group either we have it done and or we will see what happened ' ".
