The Blaugrana won last week's first leg 1-0 at the Camp Nou, meaning they just need to avoid defeat in the semi-final second leg at Mestalla on Thursday.
Barcelona manager Ernesto Valverde has opted for Andre Gomes instead of Coutinho, who has yet to register a goal or an assist over four appearances with the Blaugrana thus far.
Gerard Pique makes the starting line-up after shaking off a knee problem, and he will start alongside Samuel Umtiti in the centre of Barca's defence.
Thomas Vermaelen is still out injured for Barcelona while January signing Yerry Mina is on the bench, still looking to make his Blaugrana debut.
Barcelona XI: Cillessen; Roberto, Pique, Umtiti, Alba; Busquets, Iniesta, Rakitic, Gomes; Suarez, Messi
Subs: Ter Stegen, Vidal, Mina, Semedo, Coutinho, Paulinho, Alcacer
Valencia XI: Jaume, Montoya, Paulista, Garay, Gaya, Kondogbia, Parejo, Coquelin, Rodrigo, Zaza, Vietto
Subs: Neto, Guedes, Lato, Maksimovic, Mina, Vezo, Soler