Peters, 53, was 137-138-53 in four seasons with the Hurricanes, who said the search for a new coach will begin immediately.
"I want to thank [principal owner] Tom Dundon, [owner] Peter Karmanos and [president of hockey operations] Ron Francis for the trust they put in me to lead the team," Peters said. "This business requires hard work and long hours, and I greatly appreciate the efforts of the many people I have worked alongside during the past four years.
"We enjoyed our time in Raleigh, and my family will always feel a connection to North Carolina. I feel like this is a good time to move on, and I am looking forward to my next challenge."
Peters had one year remaining on his contract and an opt-out clause he needed to exercise by Friday.
Carolina was 36-35-11 this season, 14 points behind the New Jersey Devils for the second wild card into the Stanley Cup Playoffs from the Eastern Conference. The Hurricanes have not qualified for the postseason since 2009.
"I have a lot of respect for Bill as a person and coach," said Dundon, who took over as majority owner Jan. 11. "We thank him for his time with the Hurricanes and wish him success in whatever comes next."
Peters will coach Canada at the 2018 IIHF World Championship. He won gold as Canada's coach at the 2016 tournament.
The Calgary Flames, Dallas Stars and New York Rangers also do not have a coach.
