The pair were named to the posts Wednesday, with the honour especially significant for Alfredsson, considering the game will be played at Ottawa's Scotiabank Place on Jan. 29.
Alfredsson and Chara were selected by their fellow all-stars and as captains will set their team rosters for both the skills competition and the game at a draft Jan. 26.
The all-star squads will be designated as Team Alfredsson and Team Chara. Alfredsson's squad will wear white jerseys and red pants, while Chara's team will wear blue.
"I think both are well-deserved," said Rob Blake, who is part of the NHL's executive hockey operations department and is overseeing the organization of the all-star game. "A lot goes into the players' references on who they thought would be good leaders on the team. I think being in Ottawa with Daniel Alfredsson was kind of a for sure right from Day 1 — he's represented the league and the Senators for so many great years. "
Alfredsson is in his 16th NHL season, all with Ottawa. The 39-year-old Swede will make his sixth career all-star appearance.
The 34-year-old Chara is the captain of the defending Stanley Cup champions, but spent four seasons with Ottawa before signing with the Bruins. The towering six-foot-nine, 255-pound Slovakian will also make his sixth all-star appearance.
"I think it's an interesting storyline with Zdeno Chara — obviously being part of the Stanley Cup champions last year and the year that they're having this year, and also starting his career there in Ottawa has a little bit of intrigue," Blake said. "I think they'll do a great job and there'll be a lot of excitement around them."
Each team will have one assistant captain named next week.