[1] At thirteen, Rice was asked to take charge of a large school in Spartanburg County, South Carolina.

After one year of running the school, Rice's parents sent her to the Benedict Institute in Columbia, South Carolina, to continue her own education.

[2] Rice then served as principal of public schools in Glenn Springs, South Carolina, for three years.

In 1893, Mary Rice Phelps was elected assistant principal of Cleveland Academy in Helena, but she left within a year to accept a position at the Haines Industrial School in Augusta, Georgia.

[1][2] Phelps was also known as an accomplished writer, and James T. Haley included her essay "The Responsibility of Women as Teachers" in his Afro-American Encyclopaedia (1895).