Origi, Rossiter and Sakho have also been handed their first starts of the season.
The Reds take on Ligue 1 side Bordeaux in their opening Europa League group stage game of the season.
Liverpool reached the Europa League Round of 32 last season and while Can did feature in the campaign he was deployed as a defender in Brendan Rodgers back-three.
Can has made five appearances in the Premier League for the Reds this season and started in the 3-1 defeat against rivals Manchester United on the weekend.
Bordeaux: Carrasso, Gajic, Pablo, Pallois, Poundje, Chantome, Maurice-Belay, Khazri, Rolan, Saivet, Crivelli
Subs: Prior, Yambere, Guilbert, Traore, Poko, Kiese Thelin, Jussie
Liverpool: Mignolet, Gomez, Toure, Sakho, Moreno, Rossiter, Can, Ibe, Lallana, Coutinho, Origi
Subs: Bogdan, Firmino, Ings, Brannagan, Randall, Cleary, Chirivella