Picked by their fellow All-Stars, they will lead the team selection process at the Jan. 26 draft.
The league said Wednesday that Team Alfredsson would wear white jerseys and red pants, with Team Chara in dark blue jerseys and pants.
Alfredsson is in his 16th NHL season, all with Ottawa. The right wing has been the Senators' captain since 1999-2000, the league's longest active streak. The 39-year-old Swede will make his sixth All-Star appearance at the Jan. 29 game.
In his 14th NHL season, Chara is also making his sixth All-Star appearance. The 34-year-old defenseman from Slovakia spent four seasons with the Senators from 2001-02 through 2005-06.