The Senators confirmed on Twitter that Alfredsson will skate with the team prior to their game against the New York Islanders at Canadian Tire Centre.
Alfredsson will announce his retirement during the day Thursday.
The Senators sought and received special permission from the NHL to allow Alfredsson, a player who's not under contract, to take part in warm-ups, a league spokesman said.
"I think if he was out in warm-ups and I was playing with him, I'd probably try to convince him to stick around," former Senators teammate and current Dallas Stars centre Jason Spezza said in Toronto. "I don't know how that's going to go. I'll definitely be watching, for sure, from afar."
Alfredsson will also take part in a ceremonial faceoff before the game.
Back problems kept the longtime Senators captain from continuing his playing career, something he would have done with the Detroit Red Wings.
The 41-year-old winger spent 17 seasons with Ottawa before signing a one-year deal to join the Red Wings for the 2013-14 season.
Alfredsson had 1,157 points during his career, led the Senators to an appearance in the 2007 Stanley Cup final and won an Olympic gold medal with Sweden.
He was the captain in Ottawa from 1999 until 2013.