Rolfo, 31, volleyed home in the first half after the English club beat Valerenga last week and are fourth in the table.
Atleti are ninth in the 18-team league phase, having hammered St Poelten 6-0 eight days ago.
Both sides finished with 10 players in the Spanish capital after United's Netherlands defender Dominique Janssen and the hosts' Spanish midfielder Alexia Fernandez were shown red cards.
Two-time former Champions League winner Rolfo claimed the key goal after 27 minutes, before Janssen was sent off 10 minutes later.
Atleti's comeback efforts were hampered with a quarter of an hour to go as Fernandez was dismissed and their hopes of even a point were dashed.
Later, holders Arsenal head to Benfica, Bayern Munich host Juventus and Paris Saint-Germain welcome Real Madrid.