In the context of the modern dynamic socio-economic environment, career-related issues are becoming relevant to psychological and pedagogical sciences as it is professional development that enables people to realize their abilities, capabilities, and needs. Career orientation should be identified as early as possible in order to obtain significant achievements. An important issue is related to career orientation predictors, which determine future achievements and career choice. The study discusses conceptual provisions and methodological approaches to assessing the career orientations of college students with different levels of self-efficacy. The purpose of the research is to study theoretical and methodological approaches and aspects of the psychological assessment of self-efficacy as a personality predictor of the career orientations of college students. The study was conducted with the participation of a representative sample of 558 third-year students aged 18 to 20 on the campus of the Ural State College named after I. Polzunov (Ekaterinburg) (average age is 18.7 years). The practical significance of the study arises from the possibility to use the results obtained in order to implement programs aimed at improving self-efficacy in adolescents. The research is of practical value for organizational psychologists, educational psychologists, and teachers.