Peca began his junior career with the Sudbury Wolves of the OHL after they selected him in the first round of the 1990 player draft. He was traded to the Ottawa 67's where he blossomed into one of the leagues top offensive players. He was selected to represent Canada at the 1994 World Junior hockey tournament.

 

Peca was drafted in the 2nd round, 40th overall by the Vancouver Canucks in the 1992 NHL Entry Draft. Peca has twice won the Frank J. Selke Trophy for being the best defensive forward, in 1996-97 and 2001-02. He was a member of the gold medal-winning Canadian ice hockey team at the 2002 Winter Olympics in Salt Lake City. He was acquired by the Edmonton Oilers in a trade with the New York Islanders in exchange for Mike York.

 

Peca was part of the cinderella Edmonton Oiler team that made a run to the Stanley Cup Finals. Peca had 6 goals and 5 assists in the 2006 Playoffs.

 

On July 18, 2006, the Toronto Maple Leafs announced that they had signed Peca as a free agent to a One-year $2.5 Million dollar contract for the 2006-07 NHL season.

 

During a game against the Blackhawks on December 22, 2006, Peca collided with Chicago defenseman Jim Vandermeer in the Toronto zone with 5:17 left in the first period. Vandermeer was assessed a minor penalty and a game misconduct for the hit. While Peca went down hard and it was determined that he sustained a fractured tibia at the base of his right knee and also suffered significant ligament damage. Peca missed the remainder of the 2006-07 season.

 

On August 21, 2007, Peca signed a one-year deal with the Columbus Blue Jackets.