The Blues said Hitchcock signed a contract through the 2012-13 season.
The move to fire Payne came after St. Louis lost three of four games, falling to 6-7 on the season.
Payne was hired as the Blues' 23rd head coach before the 2010-11 season after serving as interim coach during the previous year. He guided the team to a 38-33-11 record last season -- good for 11th in the Western Conference.
He finished with a 67-55-15 mark.
Hitchcock, 59, last coached in 2009-10 for Columbus, from which he was fired in mid-season.
He led the Dallas Stars to the Stanley Cup title in 1999, and also has coaching stints in Philadelphia as well as Columbus.