Liverpool started the game well, but fell a goal behind on 14 minutes when Deco ghosted in unmarked at the far post to head home an excellent Gianluca Zambrotta cross.
The goal signaled a ten minute spell of Barcelona domination with Deco and Javier Saviola coming close to adding a second, but Liverpool weathered the storm with Jamie Carragher excellent at the back.
The Reds began to get back into the game and Craig Bellamy had a chance to equalise when Steven Gerrard whipped a free kick into the area, but his header was directed into the side netting.
Bellamy was on the score sheet two minutes before half time however, when he met a Steve Finnan cross. His header was straight at Victor Valdes but the Barcelona goalkeeper fumbled it and allowed it to squirm over the line. Valdes did push the ball out but it was to no avail as Dirk Kuyt was on hand to bury rebound, although the goal was correctly credited to Bellamy when tv replays proved his header had crossed the line.
Pepe Reina twice denied Messi with his legs and debutee Alvaro Arbeloa did well to stay on his feet to block a Messi shot wide for a corner, but in truth Barcelona did not really threaten in the second half. They were given no time on the ball by man of the match Momo Sissoko who constantly harried the Barca midfield into making mistakes.
A score draw was looking like a good result for Liverpool but fifteen minutes from the end John Arne Riise scored a priceless winner. Gerrard sent Dirk Kuyt clean through but the Dutch striker's first touch was poor and the chance appeared to have been lost. However, Bellamy picked up the headed clearance and squared the ball for Riise to fire home with his right foot.
Barcelona did hit the post late on but a draw would have been harsh on Liverpool who gave an excellent tactical performance.