Biron, who also played for the Buffalo Sabres, Philadelphia Flyers and the New York Islanders over an 18-year career, said in a Twitter post he has decided to hang up his skates.
"After thinking about it it with my family, I've decided to retire as a player and move on to a new chapter. Thank you all for your support," he wrote.
The 36-year-old Quebec native was cut loose after rough start to the 2013-14 season in a backup role to Rangers starter Henrik Lundqvist.
Biron appeared in two games as the Rangers stumbled to a 1-4-0 start, going 0-1-0 with a 7.61 goals-against average and .763 save percentage.
Had he cleared waivers, he would have been eligible to report to New York's Hartford, Conn., minor-league affiliate.
Over 508 career regular-season appearances, Biron posted a 230-191-52 record, 2.62 GAA and 28 shutouts.
He is one of only five players in NHL history to play for all three teams in the state of New York, NHL.com reported.