The Spaniard is on a season-long loan with the Eredivisie champions who will travel to the Nou Camp in midweek to take on last year's semi-finalists in their opening game in Group H.
That is followed by a clash against AC Milan, where Bojan spent last season on loan, at the Amsterdam ArenA on October 1.
The 23-year-old played more than 100 games for Barcelona between 2007 and 2011 before being sold to Roma, who subsequently loaned him to Milan, with Bojan returning to the Catalan giants this summer only to move to Holland.
Bojan admits he was taken aback by the coincidence, telling vi.nl: "When I looked at the draw, I was not even aware that this outcome was a possibility.
"I'm really looking forward to the start of the Champions League."
Bojan is under no illusions that the hosts will be overwhelming favourites on Wednesday, in a group that also features Celtic, saying: "Barca is without a doubt the best club in the world.
"We certainly do not change our tactics.
"Maybe we can change something in the details, but if you want to create a good result and chances you have to believe in your own playing style."
For Bojan, his time with Milan was clearly a learning experience. He said: "Do I regret my time in Italy?
"No, because I thought Milan at that time was the best choice for my career.
"However, football in Italy did not fit well with my playing style."