The Spain international will begin alongside Schweinsteiger in the hosts' midfield, while Pizarro is chosen ahead of Mandzukic in attack
Javi Martinez will make his first start as a Bayern Munich player after he was picked to partner Bastian Schweinsteiger in midfield for their Champions League clash against Valencia, in a rematch of the 2001 final.
The summer signing from Athletic Bilbao has already made two appearances in the Bundesliga as a substitute, and has beat out competition from Luis Gustavo to make his Champions League bow against familiar opponents from his La Liga days.
Juup Heynckes also opted for Claudio Pizarro to lead the line ahead of Mario Mandzukic, with first choice striker Mario Gomez a long-term absentee after undergoing ankle surgery in August.
The match comes too soon for Valencia midfielder Fernando Gago, who only returned from hospital on Monday after picking up a head injury while on international duty with Argentina.
With midfielders Ever Banega and David Albelda also sidelined, Mauricio Pellegrino has persevered with Daniel Parejo and Tino Costa in the Valencia engine room.Bayern Munich (4-2-3-1): Neuer; Boateng, Dante, Badstuber, Lahm; Javi Martinez, Schweinsteiger; Robben, Kroos, Ribery; Pizarro.
Subs: Starke, Shaqiri, Muller, Gustavo, Mandzukic, Can, Tymoshchuk.
Valencia (4-4-2): Alves; Pereira, Costa, Rami, Cissokho; Feghouli, Costa, Parejo, Guardado; Jonas, Soldado.
Subs: Guaita, Barragan, Victor Ruiz, Viera, Bernat, Portuges, Valdez.