The Giallorossi are the invited opposition for the annual Joan Gamper trophy match, which celebrates its 50th year this week.
And Totti is relishing the chance to go toe-to-toe with the European champions and their boss, who managed Roma in the 2011-12 season.
"I'm very happy to play against the champions of Europe, it will be a great game," said the veteran forward, speaking via AS's preview video.
"It's very stimulating and a pleasure to play against great players and, above all, a great coach in Luis Enrique.
"See you soon, coach!"
Totti has always been an outspoken supporter of Luis Enrique, despite the former Spain international enduring a disappointing campaign in charge at the Stadio Olimpico.
"We have had a great relationship from the beginning. I put myself at his disposal and he counted on me," Totti said in 2012.
"He's a great person. He wants to bring a new mentality, to try new ideas. Although at first I wasn't happy with the position I played, he was right: I enjoyed myself, as did the team and the fans."