Van Bommel, who represented both clubs during his career, favours the Spanish side in the two-legged clash.
"In such an evenly-balanced tie, [playing the second leg at home] could be decisive," Van Bommel told FCBarcelona.net.
"Barca have a very good team and have appeared in six consecutive semi-finals, which says a lot.
"We're going to see two great matches. We're going to have a real treat. They are very similar teams, they have the same style of play, they like to pass the ball and are strong in attack."
The first leg between Barcelona and Bayern Munich takes place on Tuesday evening.