The opener of the UEFA Champions League Group B will see Barcelona clash with PSV Eindhoven, on Tuesday at Camp Nou stadium.
Barcelona have won there matches against Deportivo Alaves, Real Valladolid, Huesca and Real Sociedad in their first four matches of the Laliga season.
The Catalan giants will surely be putting all efforts together so has to break the record of their rivals in the Champions having seen them claim the last three trophies.
Barcelona have not won the European Cup since 2015, and got eliminated by Roma in the quarter finals last season.
Sergio Busquets and Philippe Coutinho were left out of their Saturday campaign by the Barcelona boss, Valverde, but are expected to return to the starting line up for this match.
Dembele, has scored in each of his last three appearances for Barcelona, and will be looking forward to make an impact with his team in the Champions League.
PSV will head into the match following a 7-0 win over ADO Den Haag in the league at the weekend.
Barcelona possible starting lineup: Ter Stegen; Roberto, Umtiti, Pique, Alba; Busquets, Coutinho, Rakitic; Dembele, Suarez, Messi.
PSV possible starting lineup: Zoet; Dumfries, Schwaab, Viergever, Angelino; Rosario, Pereiro, Hendrix; Lozano, L de Jong, Bergwijn
The kick-off time is 9pm on Tuesday.