Valencia, the 2000 and 2001 runners-up who finished fourth in La Liga last season, came through qualification by beating Monaco 4-3 over two legs but were brought abruptly down to earth in the first half at their Mestalla stadium by a pair of thunderous Hulk efforts.
The Brazil forward opened the scoring in the ninth minute when he sped clear on the left and cracked a shot across goalkeeper Jaume Domenech into the far corner.
His second shortly before halftime was even better as he picked up the ball outside the penalty area and smashed it high into the net.
Valencia fullback Joao Cancelo, who hit the post in the second minute, pulled a goal back for the home side 10 minutes into the second half and forward Andre Gomes levelled 17 minutes from time when he netted from a tight angle.
Zenit’s Belgium midfielder Axel Witsel grabbed what proved to be the winning goal for the visitors three minutes later with a powerful low strike.
Zenit’s victory meant their coach Andre Villas-Boas won the battle of the Portuguese coaches as Valencia are managed by Nuno, with whom Villas-Boas worked at Porto under current Chelsea manager Jose Mourinho.
In Wednesday’s other Group H game, Olympique Lyonnais and Ghent drew 1-1 in Belgium.
(Writing by Iain Rogers in Madrid, editing by Pritha Sarkar)
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