Coach Pete DeBoer announced the appointment after practice on Thursday, adding that Patrik Elias and Ilya Kovalchuk will remain the alternate captains.
Salvador replaces Zach Parise, who signed with Minnesota as a free agent after last season.
Salvador, who signed a three-year, $9.5 million pact in July, had four goals and 14 points in the postseason after a regular season in which he failed to find the net once. He teamed up with Marek Zidlicky to form the Devils' top defensive pairing.
Salvador played all 82 regular-season games for the Devils last season, a year after missing the entire season with a rare, inner-ear concussion.