Zinedine Zidane names Karim Benzema up front alongside the Welsh striker, who has been subject of strong rumours over his future in the last 24 hours.
Cristiano Ronaldo, who has just returned from an extended summer break following Portugal's exploits at the Confederations Cup, starts the game among the substitutes.
For United, manager Jose Mourinho names a strong starting XI against his former side as he bids to lead the first English side to triumph in this game since Liverpool in 2005.
Summer signing Romelu Lukaku is picked to lead the line, with attacking support from Paul Pogba, Jesse Lingard and Henrikh Mkhitaryan, while Nemanja Matic makes his competitive debut for the side since joining from Chelsea, linking up with Ander Herrera.
De Gea, who has repeatedly been linked with a move to Madrid over the last few transfer windows, is named between the sticks.
Real Madrid: Navas; Carvajal, Ramos, Varane, Marcelo; Modric, Casemiro, Kroos, Isco; Benzema, Bale
Subs: Casilla, Nacho, Ronaldo, Theo, Vazquez, Asensio, Kovacic
Manchester United: De Gea; Valencia, Lindelof, Smalling, Darmian; Matic, Herrera; Pogba, Mkhitaryan, Lingard; Lukaku
Subs: Romero, Blind, Carrick, Fellaini, Mata, Martial, Rashford
Keep up with all of the action from Skopje tonight with Sports Mole's live text commentary here.