The move comes one day after the NHL and union reached an agreement that allows teams to buy out the contracts of unwanted players.
With the modification, teams are able to exercise an "accelerated buyout" before the start of the regular season on Saturday.
Gomez is expected to clear waivers by Thursday noon ET, thus giving Montreal the option to buy him out. He will then become a free agent.
New York Rangers defenceman Wade Redden was also placed on waivers for the purpose of being bought out, according to reports.
Gomez had a disappointing 2011-12 season, with only two goals and nine assists in 38 games.
Habs general manager Marc Bergevin announced on Sunday at the opening of the team's training camp that Gomez would not take part in the 2013 season and that they would buy out the remaining of his contract.
Gomez carries a $7.3-million US cap hit that will count against the Canadiens' salary cap this season.
As per the NHL's new collective bargaining agreement, the cap will drop $10 million in 2013-14, with teams allowed two buyouts to help fit under the cap after this season or the following.
However, with the new modified agreement, a team using a compliance buyout on a player making at least $3 million before the season begins on Saturday will only have one remaining for next summer.