In 1882, Calkins entered into Smith College as a sophomore. She studied for the year, but in 1883 with the death of her sister she took the year off from college and studied on her own. She then returned to Smith College in 1884 to graduate with a concentration in classics and philosophy.
Upon graduation, Calkins and her family took a sixteen month trip to Europe. When she returned to Massachusetts, her father set up an interview with the President of Wellesley College, an all women's college, for a tutoring job. She worked as a teacher in the Greek department for three years until a professor in the Psychology department took notice of Calkins' excellent teaching and offered her a teaching position, as long as she studied psychology for a year prior to teaching. Mary accepted the position and began to look for places to expand her knowledge of psychology.
There were not many options for women at the time looking for a place to study and graduate with a degree in psychology. Calkins decided to take classes at Harvard Annex, taught by Josiah Royce. Royce influenced Calkins to take regular classes through Harvard, taught by William James, w/ males as her peers. The president of Harvard, Charles William Eliot, was opposed to this idea; a woman learning in the same room as a man. With pressure from James and Royce, along with a petition from Mary's father, Eliot finally gave in and allowed Calkins to study in the regular classes, w/ the stipulation that she was not to be a registered student. The next few years, Calkins continued to excel in the field of psychology, working on more graduate work.
On her work with James: I began the serious study of psychology with William James. Most unhappily for them and most fortunately for me the other members of his seminary in psychology dropped away in the early weeks of the fall; and James and I were left not, as in Garfield's vision of Mark Hopkins and himself, at either end of a log but quite literally at either side of a library fire. The Principles of Psychology was warm from the press; and my absorbed study of those brilliant, erudite, and provocative volumes, as interpreted by their writer, was my introduction to psychology. What I gained from the written page, and even more from tete-a-tete discussion was, it seems to me as I look back upon it, beyond all else, a vivid sense of the concreteness of psychology and of the immediate reality of "finite individual minds" with their "thoughts and feelings. James's vituperation of the "psychologist's fallacy" -- the "confusion of his own standpoint with that of the mental fact about which he is making his report" -- results directly from this view of introspection as immediate experience and not mere inference from experience. From introspection he derives the materials for psychology. "Introspective observation," he expressly asserts, "is what we have to rely on first and foremost and always...."