The Welsh winger drops to the bench in favour of Isco as the two-time defending champions meet the Ligue 1 leaders at Santiago Bernabeu.
Madrid right-back Dani Carvajal is suspended for the match, with Nacho drafted into the team in his place.
For PSG, club captain Thiago Silva has been benched, with Marquinhos and Presnel Kimpembe preferred in the centre of the French side's defence.
Yuri Berchiche starts at left-back with Layvin Kurzawa still unavailable due to a thigh injury.
In midfield, Giovani Lo Celso has been given his first Champions League start, as the Argentine is preferred over Lassana Diarra with Thiago Motta out injured.
Real Madrid XI: Navas; Nacho, Varane, Ramos, Marcelo; Modric, Casemiro, Kroos; Isco; Benzema, Ronaldo.
Subs: Casilla, Bale, Hernandez, Vazquez, Achraf, Asensio, Kovacic
PSG XI: Areola; Alves, Marquinhos, Kimpembe, Berchiche; Lo Celso, Rabiot, Verratti; Mbappe, Cavani, Neymar.
Subs: Trapp, Di Maria, Thiago Silva, Diarra, Meunier, Pastore, Draxler