Williams, a Hurricanes' captain who turns 38 next month, announced his decision in an email from the team Monday.
"This is the first time in my life that I've felt unsure of my aspirations with regards to hockey," said Williams. "For as long as I can remember, my whole off-season until this point has been hockey and doing what was necessary to prepare for the upcoming season. Because of my current indecision, and without the type of mental and physical commitment that I'm accustomed to having, I've decided to step away from the game.
"It's important to me that the focus of attention is on the current, very talented group the Carolina Hurricanes have assembled, as they prepare to build on the momentum and growth we established last season."
Williams has played 18 seasons in the league and won Stanley Cups with the Hurricanes and Los Angeles Kings. Williams has played seven seasons in Raleigh and was named captain last year. Last season, the Hurricanes reached the playoffs for the first time since 2009.