Emelin is one of 30 players -- one from each current team -- selected by Vegas general manager George McPhee to form the expansion club's first-ever roster ahead of the 2017-18 campaign.
The 31-year-old defenseman was among a list of 23 unprotected Habs available to the Golden Knights on Wednesday.
Emelin spent his entire career with the Canadiens, after originally being selected in the third round -- 84th overall -- at the 2004 Draft. He made his NHL debut in 2011, registering 14 goals, 58 assists, and 1,236 hits in 380 regular season games since then.
The Russian rearguard notably led the Canadiens in hits during each of his six seasons in Montreal, in addition to finishing ninth among all NHLers in that category twice in 2015-16 and 2016-17.
He added another goal, five assists, and 102 hits in 29 career playoff games between 2013 and 2017.
Emelin becomes the first Canadiens player to be selected in an expansion draft since Turner Stevenson and Frederic Chabot were lost to the Columbus Blue Jackets, in 2000.
