The 31-year-old insists the Copa del Rey champions must not make mistakes if they want to win the Supercopa and said he plans to celebrate if he scores
The Liga champions take on the Rojiblancos for the first piece of Spanish silverware this season on Wednesday and Villa - who moved from Camp Nou to Vicente Calderon this summer - believes that victory over two legs is feasible if they keep errors out of their game.
"Atletico will have many chances to win, but for that to happen we have to do everything perfect," he told reporters.
"We can't make mistakes, play well at the back, try to keep the ball as long as possible - because we know that Barc suffer when they lose the ball - and then we can take our opportunities in attack
"If you have to look for a favourite, it is Barcelona. We have to fight against that. When the match starts, we all have the same chance to win.
"Just look at the statistics of recent years and the way they have started the league. We must seek our options and how we can hurt them. Lifting this title is very important to us."
Villa insists he will put all friendship aside when he faces his former team-mates and says he plans to celebrate against the Blaugrana should he score in Wednesday's home leg.
"I have many friends and fond memories of my three years there, but when we start the game, they are my rivals.
"Hopefully I can help my team. I have always celebrated my goals. Out of respect, however, the exuberance of the celebration is different if you face an opponent that you love."
Villa acknowledges that Gerardo Martino's side will be the heavy favourites for the clash, especially following their resounding 7-0 win over Levante on Sunday, but the 31-year-old remains determined to upset the odds.