Kovalchuk, 30, said he planned to return to Russia so he could spend more time with his family. He had played the last four seasons with the New Jersey Devils.
"After many conversations with Ilya over the past year on his desire to retire from the National Hockey League, Ilya's decision became official today," Devils CEO and General Manager Lou Mamoriello said.
"On behalf of the entire organization, I wish Ilya and his family all the best in their future endeavors."
During the lockout-shortened 2013 campaign Kovalchuk had 11 goals and 20 assists.
"This decision was something I have thought about for a long time going back to the lockout and spending the year in Russia," Kovalchuk said in a statement released by the team.
"Though I decided to return this past season, Lou was aware of my desire to go back home and have my family there with me. The most difficult thing for me is to leave the New Jersey Devils, a great organization that I have a lot of respect for, and our fans that have been great to me."
Kovalchuk was chosen by Atlanta with the first overall selection in the 2001 NHL draft. He was traded to the Devils on Feb. 4, 2010.