The acquisition of Jeremy Roenick and Jiri Dopita by the Flyers in the summer of 2001 left Langkow, a restricted free agent, as the odd man out in Philadelphia. He was dealt to the Phoenix Coyotes in exchange for a second-round draft pick in the 2002 NHL Entry Draft (Dan Sprang) and a first-round pick in 2003 (Jeff Carter). Unable to agree on a contract, Langkow and the Coyotes went to arbitration where he was awarded a two-year contract worth $4.2 million. He made an immediate impact with Phoenix, scoring his first career hat trick in a 5–2 victory over the Washington Capitals in the Coyotes' home opener. He finished the 2001–02 season as the team leader with 62 points. He fell back to 52 points in 2002–03, but scored his 100th career goal in his 500th career game on December 30, 2002, a 4–3 overtime victory against the Edmonton Oilers. He finished second in team scoring with 52 points, and served as an alternate captain for the Coyotes during the 2003–04 season.