Alice Barber was born near Salem, New Jersey. She was the eighth of nine children born to Samuel Clayton Barber and Mary Owen, who were Quakers.
She attended local schools until she and her family moved to Philadelphia, Pennsylvania. At age 15 she became a student at the Philadelphia School of Design for Women (now Moore College of Art & Design), where she studied wood engraving.
She was admitted to the Pennsylvania Academy of the Fine Arts in 1876 (the first year women were admitted), studying under Thomas Eakins. Among her fellow students at the Academy were Susan MacDowell, Frank Stephens, David Wilson Jordan, Lavinia Ebbinghausen, Thomas Anshutz, and Charles H. Stephens (whom she would marry).[6] During this time, at the academy, she began to work with a variety of media, including black-and-white oils, ink washes, charcoal, full-color oils, and watercolors. In 1879, Eakins chose Stephens to illustrate an Academy classroom scene for Scribner's Monthly. The resulting work, Women's Life Class, was Stephens' first illustration credit.