The summer signing from Paris Saint-Germain earns a spot in the starting XI at right-back as Mauricio Pochettino makes three changes following the 3-0 victory at Everton on Saturday.
Kieran Trippier and Moussa Sissoko drop down to the bench as Mousa Dembele joins Eric Dier and Ben Davies in midfield, while Dele Alli's suspension for seeing red in the Europa League game against Gent last term means that Son Heung-min earns a recall alongside Christian Eriksen and Harry Kane in the attack.
For Dortmund, Peter Bosz makes five changes following the goalless stalemate at Freiburg in the Bundesliga on Saturday as he utilises a squad depleted by injuries.
Andriy Yarmolenko earns his first start for the club, coming in for Maximilian Philipp in a frontline alongside Pierre-Emerick Aubameyang and Christian Pulisic.
Tottenham Hotspur: Lloris; Aurier, Alderweireld, Sanchez, Vertonghen; Davies, Dier, Dembele; Eriksen, Son, Kane
Subs: Vorm, Foyth, Trippier, Walker-Peters, Winks, Sissoko, Llorente
Borussia Dortmund: Burki; Piszczek, Sokratis, Toprak, Toljan; Sahin, Dahoud, Kagawa; Aubameyang, Yarmolenko, Pulisic
Subs: Weidenfeller, Subotic, Castro, Gotze, Zagadou, Isak, Philipp
Keep up with all of the action from Wembley this evening with Sports Mole's live text commentary here.