The Oilers signed Ference, 34, to a four-year deal worth $13 million US per season. It represents a raise of $1 million per season over his expiring contract with Boston.
Edmonton soon after the Ference move announced the signings of recent Phoenix players Boyd Gordon and Jason LaBarbera.
Ference has played in three Stanley Cup finals, winning with the Bruins in 2011. In addition to Boston's appearance in the final last month, the blue-liner was with Calgary when they lost in the 2003 final to Tampa Bay.
Boston, with salary cap pressures and more than a couple of young defencemen on the horizon, opted to not re-sign Ference. The Bruins had obtained him in February 2007 in a multi-player trade with the Flames.
Originally drafted by Pittsburgh in 1997, Ference has recorded 37 goals and 156 assists in 760 career regular season games, with 645 penalty minutes.
Edmonton earlier acquired defender Philip Larsen from Dallas in a trade that saw veteran Shawn Horcoff head to the Stars.
Defensive forward Gordon, who can play right wing or centre, has 39 goals and 83 assists in 486 NHL games spent with Phoenix and Washington. Gordon, who will turn 30 in October, signed a three-year deal.
Labarbera signed a one-year contract. The veteran backup spent the last four seasons with the Coyotes and has six shutouts in 175 career games, with stops also with Vancouver, the New York Rangers and Los Angeles.
He has a career average of 2.84, with a .909 save percentage.