Between 1852 and 1868, he served as headmaster of high schools at Dorchester, Lawrence, Salem, and Cambridge, Massachusetts.

[3] Early in his career, he edited selections from Ovid and Virgil and (in collaboration) the Cambridge Course of Physics (six volumes, 1867–68).

Rolfe's editions proved to be the best-selling versions in America (during a time of increased use of Shakespeare in high school classrooms) due both to his credentials as a high school administrator and to his use of Bowdlerization of the text in order to remove much of Shakespeare's lewd content.

He wrote a very useful Satchel Guide to Europe, revised annually for 35 years, and at least five other books: He married Eliza Jane Carew in Dorchester on July 30, 1856.

[6] William James Rolfe died on July 7, 1910, at the home of a son in Tisbury, Massachusetts.