The homer put Philadelphia ahead for good after a 2-0 deficit.
Aaron Rowand added an RBI single in the top of the eighth and Rollins had three of the eight hits for the Phillies, who have won four of their last five games.
Winner Adam Eaton (6-4) yielded two earned runs on five hits and two walks in six innings. He struck out four. Antonio Alfonseca earned his third save.
The loser was reliever Aaron Heilman (5-3). Mets starter Orlando Hernandez scattered three hits over six scoreless innings with four walks and three strikeouts.