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.
Celebrity Families of 2014 [PHOTOS]