The Belgium international made his belated first competitive appearance for the club on the final day of the previous Liga season after battling a thigh injury throughout his first campaign at the Catalan giants.
Vermaelen, who arrived at Camp Nou in August 2014, suffered another setback at the beginning of 2015-16 but the former Arsenal captain says he is fired up for his first appearance in the tournament with the European champions.
"It'll be something very special, I'm looking forward to it," he said.
"I understand people might question how I feel. When I'm on the pitch I don't feel that I'm scared of getting injured again.
"The small setback was disappointing but I feel good."
Barcelona have struggled for defensive consistency so far this season but Vermaelen feels the whole team must accept responsibility.
"Defending is about a team, the shape of the team. It's an important part of the game," he said.
"I agree there are a lot of players who can play [at centre-back]. But we know there are a lot of games and we need all our players, all the squad.
"I think we all want to play the same, we want to fit into the role as well as we can with the qualities we have. We all want to play with the ball, as Barcelona does.
"I know we haven't done that as well as last season in a few games. The team is working on the training pitch."