With Philadelphia trailing 2-1, Rollins led off the fifth inning by cranking a 1-0 pitch from Edwin Jackson over the left-field fence -- his second solo blast of the game.
Schierholtz, obtained from San Francisco Tuesday for Hunter Pence, followed by putting another Jackson pitch into the left field stands, and the Phillies went to clinch their three-game series.
Vance Worley (6-6) went seven innings to collect the win, yielding two unearned runs on six hits. The right-hander issued one walk.
Jonathan Papelbon secured the victory with his 23rd save.
Jackson (6-7) allowed three runs on eight hits, going 5 2/3 innings for the National League East-leading Nationals.
Adam LaRoche and Danny Espinoza drove in Washington's runs.