Her education was very important to her and her parents.  She studied to become a surgeon at Syracuse Medical College and graduated in 1855 with a medical degree. After college she met Albert Miller, also a physician, and they got married in 1856 but she kept her last name as Walker.  After marriage, together they started a medical practice, but not many people wanted to go to a woman doctor as they did not trust she could do as good of a job as a man physician. The practice struggled and so did the young couples marriage. Thirteen years later Mary Walker and Albert Miller divorced and their practice failed. Although her marriage failed, she came back more confident than ever as the Civil War began.