Valencia were deservedly beaten by Bayern Munich – but gave the Germans a scare in a dramatic finale at the Allianz.
This was a game imbued with personal significance for Valencia boss Mauricio Pellegrino, who missed the decisive penalty in the shoot-out when Bayern defeated Los Che in the Champions League Final 11 years ago.
The hosts were able to call upon Arjen Robben – who won his race to be fit – and Javi Martinez, the former Athletic Bilbao man making his first start for the Germans since his €40m summer switch.
Pellegrino made three changes from the weekend win over Celta Vigo, reintroducing Joao Pereira, Ricardo Costa and Andres Guardado.
Strangely both sides donned their away strips, Bayern all in black, Valencia in the yellow, red and blue of the 'Senyera', the flag of the Valencian community.
The 'Robbery' double act threatened to break into Valencia's defence in the 14th minute, Franck Ribery just failing to connect with an enticing cross from fellow wingman Robben.
Toni Kroos wriggled into space on the edge of the box soon after, his stinging low left foot shot parried by Diego Alves.
A corner fell to Dante, but Ricardo Costa got in the Bayern centre-back's way to block his header.
Valencia were defending well but seeing alarmingly little of the ball, and duly fell behind in the 38th minute.
Ribery sprinted down the left and pulled back for Robben, whose smart reverse pass set up Bastian Schweinsteiger to rifle an angled drive into the bottom left corner. The shot took a deflection off Aly Cissokho.
Valencia showed much more attacking intent in the opening stages of the second half, Cissokho's swerving cross and Tino Costa's low shot both forcing Manuel Neuer into action.
Kroos again unloaded from the edge of the area, but again Alves proved equal, tipping over the bar.
Valencia had an excellent chance when Sofiane Feghouli barged past Dante, but his effort flicked off the toe of Bayern's Jerome Boateng and wide.
But just as Valencia were coming into it, Bayern doubled their lead, Kroos finally getting the better of his personal duel with Alves by smacking a stunning 25 yarder into the top corner.
The game seemed to be coasting to a conclusion but there was a dramatic finale in store.
Substitute Nelson Valdez pulled one back for Valencia with a downward header from Jonathan Viera's cross.
Bayern then raced up the other end and won a penalty, Adil Rami shown a second yellow and red for hauling down Robben, but Mario Mandzukic's spot kick was saved by the outstanding Alves.
Bayern Munich 2 Valencia 1
Scorers: Schweinsteiger 37 (BM), Kroos 76 (BM), Valdez 91 (V)
Bayern Munich: Neuer; Boateng, Dante, Badstuber, Lahm; Javi Martinez (Luis Gustavo 69), Schweinsteiger; Robben, Kroos, Ribery (Muller 46); Pizarro (Mandzukic 63)
Valencia: Diego Alves; Pereira, Ricardo Costa, Rami, Cissokho; Tino Costa, Parejo; Guardado (Viera 71), Feghouli, Jonas (Valdez 63); Soldado (Barragan 88)
Sending off: Rami 93 (V)
Missed pen: Mandzukic 94 (BM)
Ref: Aydinus (TUR)