The veteran centre signed a US$700,000, one-year contract with the Coyotes on Sunday.
Perreault had a career-high 57 points with the Nashville Predators last season before becoming an unrestricted free agent. The 35-year-old entertained offers from other teams before signing with Phoenix.
He joins a Coyotes team that is last in the Western Conference after a 3-9-0-0 start.
Perreault was originally selected 47th overall by Toronto in the 1991 draft. In 740 games with the Maple Leafs, Los Angeles, Montreal and Nashville, he has 217 goals and 464 points.
Perennially one of the league's best faceoff men, Perreault has won 61.7 per cent of draws in his career.