Panathinaikos took the lead against the run of play through Sidney Govou in the 20th minute but Barca hit back in merciless fashion to take a 3-1 lead by half-time through two goals from the irrepressible Messi and another from David Villa.
Messi, having also hit the crossbar in the first half, spurned the chance to net his hat-trick in the 55th minute when his weak penalty was saved by Alexandros Tzorvas, but teed up Pedro and Daniel Alves for further goals.
A weakened Manchester United team could only draw 0-0 with Rangers in their opening Champions League tie as Antonio Valencia suffered what appeared to be a serious injury.
United made ten changes from the side that drew with Everton at the weekend and failed to carve out enough chances at Old Trafford when being frustrated with a defensive Rangers side.
Barcelona's David Villa (R) celebrates with teammate Lionel Messi after scoring against Panathinaikos during their Champions League Group D soccer match at Nou Camp stadium in Barcelona September 14, 2010.
Midfielder Valencia was taken to hospital after suffering what appeared to be a broken leg in the second half following a challenge from Kirk Broadfoot. The Ecuadorian required oxygen on the pitch when he was carried off the pitch.
Tottenham's first ever Champions League game started superbly when an own goal from Petri Pasanen and a towering header from Peter Crouch put them 2-0 up against Bremen, but they were held to a 2-2 draw in Bremen.
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