The Argentine is chosen to lead the line for Los Blancos ahead of Karim Benzema, while the French defensive midfielder is preferred to Sami Khedira in the middle of the park
The Argentine has impressed in pre-season and will start the match with support from Cristiano Ronaldo, Mesut Ozil and Angel Di Maria in the Blancos attack.
Jose Mourinho has also sprung a surprise in midfield, with Lassana Diarra having been preferred to Sami Khedira, who was a regular starter for the Spanish champions alongside Xabi Alonso last season.
Valencia start the match with two ex-Real Madrid stars in their starting XI. Roberto Soldado leads the line for the visitors and new summer signing Fernando Gago starts in the engine room alongside Tino Costa.
Elsewhere, Ricardo Costa will partner Victor Ruiz at the back, while new recruit Joao Pereira will begin the match at right-back.
One of Mauricio Pellegrino’s other summer signings, Andres Guardado, is also handed a debut and will feature on the left-side of the attacking quartet.Real Madrid (4-2-3-1): Casillas; Arbeloa, Pepe, Ramos, Coentrao; Alonso, Diarra; Di Maria, Ozil, Ronaldo; Higuain.
Subs: Khedira, Kaka, Benzema, Marcelo, Adan, Albiol, Callejon.
Valencia (4-2-3-1): Alves; Pereira, R. Costa, Ruiz, Mathieu; T. Costa, Gago; Feghouli, Jonas, Guardado; Soldado.
Subs: Rami, Albelda, Piatti, Barragan, Valdez, Parejo, Felipe.