The 31-year-old brought an end to his trophy-laden three-year stay with the Camp Nou club in order to seal a switch to the Spanish capital in July.
And he faces an immediate reunion with the Catalans when the Copa del Rey holders host the 2012-13 Liga champions in the first leg of the Supercopa on Wednesday.
However, the Spain international has denied suggestions that he will go easy on Barca and says he will always be happy to score goals no matter who the opposition.
"This isn’t the first time that I have faced former team-mates and friends. I have very good friends there but when you start the game it will be the same for us and them, as always," he said.
"Will I celebrate if I score? I always celebrate goals, no matter who the opponent is, out respect I will be less effusive, but I’m not going to remain motionless."
Villa went on to talk up the importance of lifting silverware early in the season, and insisted Atletico can overcome Gerardo Martino's side.
"You never know if it is better or worse to be playing in a two-legged final. But we cannot make mistakes, we will have to do our best," he added.
“We have to be good defensively and try to take possession as that is how they suffer. We want to play well in both legs and to win the title.
"To raise a trophy in August would be very important for any team. We have to think about the first leg here at the Calderon and about taking an advantage back to theirs.
"How do you beat them? Anyone can beat anyone. More so with potential like Atletico, especially in the final stages.
"I believe that we have the options in place to beat them, but we have to do everything perfectly."
Villa scored 48 goals in 116 appearances for Barcelona, winning two La Liga titles, one Copa del Rey and one UEFA Champions League during his time at the club.
