With the scored tied at 61, Tolliver scored on a lay-up and then made a conventional three-point play with 33 seconds left to give the Saints a 66-61 lead they never relinquished.
Freshman forward Mack Spellman (Clinton, NY) added 17 points and sophomore forward Brian Lindsey (New Orleans, LA) had 11 points for the Saints who ran their winning streak to nine games.
Emmanuel (14-6) leads the conference with a 12-1 record.
The Saints led 33-31 at intermission and held a 61-51 lead with 6:12 left in the game before Western New England College went on a 10-0 run to tie the contest at 61 following a free throw by freshman guard Matt Maynard (Paterson, NJ) at the 1:32 mark.
Senior guard Jon Godbout (Bristol, CT) led the Golden Bears with 16 points while Maynard finished with 12.
Western New England College, which had won six of its last seven games, drops back to the .500 mark at 10-10. The Golden Bears are 8-5 in the GNAC.