The 30-year-old had been linked with a move away from the Bernabeu throughout the summer. Nevertheless, coach Jose Mourinho has opted to use his services in the Amsterdam ArenA tonight.
Young attacker Jose Callejon will also feature from the beginning.
Hosts Ajax will have Danish youngster Christian Eriksen in an advanced midfield role.
Ajax: Vermeer; Van Rhijn, Alderweireld, Moisander, Blind; De Jong, Poulsen, Eriksen, Sana, Babel; Boerrigte
Real Madrid: Casillas; Marcelo, Pepe, Ramos, Arbeloa; Essien, Alonso; Cristiano Ronaldo, Kaka, Callejon; Benzema