Pulford and his family lived on King St. in Weston, Ontario from 1940 to 1950, and he attended Memorial School prior to the family move to rural Ontario. Pulford played junior hockey in Weston, then senior hockey for the Marlboros.
Pulford played junior hockey for the Toronto Marlboros for three seasons from 1953 to 1956, winning two Memorial Cups under coach Turk Broda. He moved up to the Maple Leafs for the 1956–57 season and remained with the team for 14 seasons wearing jersey number 20. Pulford was an important member of the Leaf teams that won four Stanley Cups in 1962–1964 and 1967. The Leafs traded him to the Los Angeles Kings on September 3, 1970, where he played two seasons and retired as a player in 1972.
In 1967 Pulford was elected the first president of the National Hockey League Players' Association.
Pulford became head coach of the Kings for the 1972–73 season and led the team for five years before becoming coach and general manager of the Chicago Blackhawks in 1977. As coach of the Kings, he helped Los Angeles go from being one of the worst defensive and penalty killing teams in the NHL to one of the best. He guided the Kings to their first playoff appearance in five years in 1974, and won the Jack Adams Award as coach of the year in the NHL in 1975. That season, the Kings amassed 105 points, still a club record through 2013. He also led the Kings to their first playoff series wins since 1969 when they defeated the Atlanta Flames in the first round of both the 1976 and 1977 NHL playoffs. Pulford left the Kings after the 1976–77 season after constant feuding with then owner Jack Kent Cooke. Pulford wanted to become General Manager as well as coach, or at least have a bigger role in player personnel decisions. Cooke however, often meddled in player personnel matters, and in the mid-1970s, reverted to his old habits of trading promising young players and draft picks for veteran, past their prime former stars.
He served as coach for the Blackhawks on three separate occasions from 1977 to 1987. He was promoted to senior vice president in 1990, but took on the general manager's duties again from 1992 to 1997, from 1999 to 2000, and from 2003 to 2005. During his third stint as general manager, Pulford nominally doubled as head coach. However, Lorne Molleken remained the team's main operator on the bench, with Pulford as more or less a senior consultant.
In 7 seasons: 426 games as Hawks coach, Bob Pulford won 182, lost 176, and tied 68. His win percentage was .507 and he is ranked third behind Billy Reay and Joel Quenneville for most regular season games won as Hawk coach.
With the series tied 1–1, Pulford scored the overtime game winner in game 3 of the 1967 Stanley Cup Finals against the Montreal Canadiens. The Montreal goalie was Rogie Vachon. Pulford later coached Vachon in Los Angeles as the Kings rose to prominence in the mid-1970s.
He won the Jack Adams Award for best coach in the NHL in 1975. Pulford was also honoured to be named head coach of Team USA during the 1976 Canada Cup tournament.
He was inducted into the Hockey Hall of Fame in 1991.
On October 11, 2007, Pulford was named an officer with the Wirtz Corporation and is no longer part of the day-to-day management of the Blackhawks.
His son-in-law is Dean Lombardi, a former assistant general manager for the Minnesota North Stars, former GM of the San Jose Sharks, and current president and general manager of the Los Angeles Kings since April 2006.
In 2012, Pulford was honoured by the Kings in a pregame ceremony; the team wore their purple and gold 1970s throwback uniforms in the game following this ceremony.