PVAMU (1-18, 1-6) led by as many as 13 in the first half and had a 58-49 advantage with 11:37 to play before Mississippi Valley State used a 14-3 run over the next 3 1/2 minutes to take its first lead since early in the first.
The Delta Devils pushed their lead to 72-66 with 3:49 remaining but the Panthers started to apply full-court pressure and rallied to tie it at 73-all on a free throw by Jordan Giddings with 1:05 to go.
Romain missed a layup and Williams grabbed the offensive rebound and hit a short jumper 22 seconds later. After PVAMU's Jaryn Johnson missed a 3, Admassu Williams got the offensive board and was fouled, but missed both free throws.
Romain hit 1 of 2 free throws to make it 76-73 and Tevin Bellinger missed a potential tying 3 for the Panthers.
Zachary Hamilton led Prairie View with 13 points.