The 39-year-old pivot was 23-of-38 for 325 yards and three touchdowns in Montreal's 33-32 comeback win over the Calgary Stampeders.
Calvillo, who suffered an injury to his non-throwing shoulder a week earlier, came up big in the fourth quarter, completing a seven-yard TD pass to S.J. Green at 13:13, followed by a three-yard touchdown pass to Patrick Lavoie at 14:13.
Montreal teammate Jerald Brown added to the Alouettes' haul by claiming defensive honours. The defensive back intercepted Calgary quarterback Kevin Glenn with 1:36 remaining in the fourth quarter, returning it 33 yards downfield.
Alouettes linebacker Shea Emery added top Canadian honours thanks to his six tackles against Calgary.
Meanwhile, Hamilton Tiger-Cats wide receiver/kick returner Chris Williams took the special teams nod. Williams had four punt returns for 113 yards and a touchdown, one missed field goal return for a 119-yard touchdown and one reception for 34 yards for another TD in the Ticats' 36-27 win over the Toronto Argonauts.
The players of the week awards are sponsored by Gibson's Finest.