For many, college is a period of transition, marked with acute stress, threats to success, and decreases in self-efficacy. For certain groups of students, the risk of these poor outcomes is elevated. In this study, 348 students from a large residential university in the western United States were surveyed to understand the role of psychological flexibility and inflexibility on self-efficacy and the potential moderating impact of year in college and underrepresented racial minority (URM) status. Results indicated that students who are psychologically flexible reported greater college self-efficacy, whereas students who are psychologically inflexible reported lower college self-efficacy. The impact of psychological inflexibility on self-efficacy was moderated by URM status and year in school; psychological inflexibility had a stronger impact on URM students’ self-efficacy than nonminority students, and psychological inflexibility had a greater effect on college students starting college as opposed to students who had been enrolled for multiple years.