The Brazilian has previously played for the Spanish side and has admitted he has talked to his former team-mates.
“I have a great will to play against one of the best teams in the world,” Motta told Sport.
“I have spoken to some of their players. I have many friends there. We hope to have a good game, and I am hoping we can beat them.”
“I am really motivated coming back to play in the Champions League,” added the midfielder. “It would be awesome to start with a win.
“Mourinho? He always prepares for games in precise ways, and it will be a special encounter for him.
“The only way to beat [Barca] is to play better on the night.”