Luongo was expected to discuss his decision with Canucks general manager Mike Gillis after arriving in Vancouver from his Florida summer home.
"We respect and support his decision to relinquish the captaincy and are confident that he will continue to help lead our team through his tremendous character and work ethic both on and off of the ice," Gillis said in a release. "Roberto has been an excellent captain for our team."
The team said it will announce its new leadership before the season starts.
In 2008, Luongo became the first NHL goaltender in 60 years to be selected captain, but league rules prohibited him from wearing the "C'' on his jersey or acting as captain on the ice by talking to referees during games.
Instead Luongo painted a "C'' on the chin of his mask, and the Canucks designated three alternate captains — instead of the usual setup of two alternates and a captain — to take ceremonial faceoffs before game and talk to officials during them.
"I am honored to have served as captain of the Vancouver Canucks for the past two seasons," Luongo said in a release. "Being captain in a Canadian city for a team with such passionate fans is a privilege and an experience I will always take pride in. I will continue to be a leader on this team and support my teammates the same way I always have while focusing on our ultimate goal."
Before Luongo, the last NHL goaltender to serve as team captain was Bill Durnan of the Montreal Canadiens during the 1947-48 season. Rules forbidding goalies from being captain were passed prior to the following season after protests that Durnan was leaving his crease to protest calls with the officials as a way to effectively create extra timeouts for the Canadiens.