Rangers were forced to back-pedal from the start. Goalkeeper Lionel Charbonnier had to act smartly after six minutes to punch away an in-swinging corner from Gaizca Mendieta.
Rangers retaliated when Sergio Porrini picked out Claudio Reyna on the right. The American midfielder cut inside only to see his shot go narrowly over the top. It proved a brief respite for Rangers as Valencia poured forward. Tony Vidmar was forced to hack away a backheel from Claudio Lopez.
Valencia captain Mendieta then clipped a shot wide of the post following a cross from Gonzalez. Charbonnier reacted superbly to push away a shot from Gonzalez. Valencia thought they had a penalty after 21 minutes when Jocelyn Angloma and Lorenzo Amoruso tussled as Lopez's cross came in but the referee awarded a free-kick to Rangers.
Rangers got into the match and Vidmar dragged a shot wide of the post after a good run which took him past Joachim Bjorklund. Porrini then came to Rangers' rescue, steering a shot from Juan Sanchez into the path of Charbonnier.
Amato should have put Rangers ahead six minutes before the break when he headed wide in front of the posts following a freekick from Giovanni van Bronckhorst.
The Rangers manager, Dick Advocaat, decided to freshen things up at half- time and brought on Jorg Albertz for the ineffective Neil McCann.
Albertz was quickly into the action, latching on to a pass from Amato, but his cross was poor and scrambled away. Charbonnier was then booked for time wasting as Rangers continued to live dangerously. Valencia star David Albelda fired over the top and Angloma dragged his shot wide of the target.
But, in the 56th minute, Valencia made the breakthrough. A cross from Sanchez was knocked away one handed by Charbonnier but spun off team-mate Craig Moore and over the line. Five minutes later Valencia's Lopez had a goal narrowly disallowed for offside, but Gonzalez sealed the win for Valencia with a left-footed shot from 14 yards in the 74th minute.
Valencia: Canizares, Pellegrino, Bjorklund, Mendieta, Lopez, Gerard, Carboni, Sanchez, Kily Gonzalez, Angloma, Albelda. Substitutes: Palop, Camarasa, Djukic, Oscar, Angulo, Ilie, Serban.
Rangers: Charbonnier, Porrini, Moore, Amoruso, Vidmar, Reyna, Ferguson, Van Bronckhorst, Mols, Amato, McCann. Subs: Niemi, Numan, Kanchelskis, Albertz, Hendry, Adamczuk, Johansson.
Referee: Lubos Michel (Slovakia)