Brazil international Alves has yet to be given the all-clear by club medical staff due to a sore knee and missed Saturday's 2-0 La Liga win at home to Athletic Bilbao.
Although he sometimes neglects his defensive duties and prefers dashing up the wing, Alves gives Barca extra zip going forward and links well with club top scorer Lionel Messi.
"In principle, he (Alves) will play," Luis Enrique told a news conference at the Nou Camp.
"We'll see how he is tomorrow but today he trained normally like the rest of the players," added the former Barca and Spain midfielder, who is poised make his Champions League debut as coach of the Catalan giants.
Barca have made a solid start to their domestic campaign under Luis Enrique, who took over from Gerardo Martino at the end of last season.
They are the only team in La Liga to have won their opening three matches and have not conceded any goals, suggesting they may have ironed out the defensive weakness that hampered their progress last term.
Luis Enrique was cautious about reading too much into Barca's fine start but said he was "very pleased" with the way the team were defending as a unit.
"We are at the start of the season with a lot of things still to improve," he said.
"There have been positives and negatives but in general I think the team is in good shape.
"We have had a good start to the season but it doesn't mean anything. There is still a very long way to go with many games to play and many things to improve.
"For sure there will be delicate moments and we have to get through those too."
Barca's Spain centre back Gerard Pique was not at his best last season and was dropped for the Bilbao game, although he came on to replace Javier Mascherano after the Argentine took a boot to the head.
Pique has been suffering with a hip injury but said he was fit to play and would work hard to convince Luis Enrique he deserved to be in the starting team.
"Physically I am fine, training well and although the hip is not at 100 percent I can play perfectly well," he said.
"The important thing in the end is that the team wins and to just get on with it, work hard to get into the team."
Pique said he expected a defence-minded APOEL and predicted scoring early would be key to forcing the Cypriot side on to the offensive.
"They are likely to close ranks at the back and it's going to be tough to get the first goal which will make them open up and give us more scoring chances," he said.
"We are coming into the match having won our first three games without conceding a goal and playing entertaining football and we are feeling very comfortable.
"We know it's a Champions League game and we have to get the three points to start the competition with calm. Our goal is to top the group."
Ajax Amsterdam host Paris St Germain in Wednesday's other Group F game.