After winning the competition in the previous campaign, Manchester United were hoping to make a successful start to their Champions League defense with a victory over Villarreal.
United emerged victorious from a penalty shootout with Chelsea, after the two teams had drawn the first ever all-English European Cup final in a lively encounter in Moscow.
No team had ever successfully defended the trophy, so the pressure was on Sir Alex Ferguson and his side to make an impressive start at Old Trafford, but they were handed tough opposition for their opening fixture, with Spanish outfit Villarreal standing in their way.
The former Champions League semi-finalists had Robert Pires and the emerging Santi Cazorla in their ranks, while goalkeeper Diego Lopez, now with Real Madrid, was beginning his second season with El Submarino Amarillo.
Ferguson left Cristiano Ronaldo on the bench with the Portuguese winger continuing to regain fitness after an ankle injury, while Jonny Evans got the nod over Nemanja Vidic.
The home side began on top at Old Trafford, but Rio Ferdinand squandered an opportunity to give his side the lead when failing to convert the ball into the net from an Owen Hargreaves corner.
Lopez was enduring an uncertain time in the Villarreal goal, but he did keep his side level at 0-0 with timely blocks from Nani and Carlos Tevez.
The Premier League title holders looked as though they should have been awarded a penalty shortly before the interval when Park Ji-Sung was upended by Joan Capedevila, but United's strong appeals were turned down by the referee.
Villarreal returned after the break with much more vigour and threat going forward, and they almost took the lead shortly before the hour when Guillermo Franco's flick hit the post with Edwin van der Sar beaten.
That near miss for the Spanish side resulted in the introduction of Ronaldo, who was given a rapturous ovation as Ferguson gave him 25 minutes to try to turn the match in United's favour.
The Portuguese winger almost had an instant impact when a volley tested Lopez, before he helped create a chance for Tevez, which was cleared off the line.
United were rampant, and after he had headed marginally wide from a cross from Nani, Ronaldo played in a sublime delivery for Evans, who crashed his header against the post.
That opening proved to be a final chance in what had proven to be a entertaining tussle between two quality teams, despite the lack of goals at Old Trafford.
As well as Villarreal, United were drawn alongside Celtic and Danish side Aalborg, but despite the group looking a mere formality for the Red Devils, they made hard work of it, drawing on four occasions to pick up 10 points from the group.
However, Ferguson's men did qualify for the knockout stages at group winners, and they surged through to the final with victories over Inter Milan, Porto and Arsenal.
It handed them the opportunity to retain their grasp on the Champions League Trophy, but they were outclassed in Rome by Barcelona, who produced an efficient performance to come away with a 2-0 triumph.