Educational researchers have intensively investigated students" academic self-concept (ASC) and self-efficacy (SE). Both constructs are part of the competence-related self-perceptions of students and are considered to support students" academic success and their career development in a positive manner (e.g., Abele-Brehm & Stief, 2004; Richardson, Abraham, & Bond, 2012; Schneider & Preckel, 2017). However, there is a lack of basic research on ASC and SE in higher education in general, and in undergraduate psychology courses in particular. Therefore, according to the within-network and between-network approaches of construct validation (Byrne, 1984), the present dissertation comprises three empirical studies examining the structure (research question 1), measurement (research question 2), correlates (research question 3), and differentiation (research question 4) of ASC and SE in a total sample of N = 1243 psychology students. Concerning research question 1, results of confirmatory factor analysis (CFAs) implied that students" ASC and SE are domain-specific in the sense of multidimensionality, but they are also hierarchically structured, with a general factor at the apex according to the nested Marsh/Shavelson model (NMS model, Brunner et al., 2010). Additionally, psychology students" SE to master specific psychological tasks in different areas of psychological application could be described by a 2-dimensional model with six factors according to the Multitrait-Multimethod (MTMM)-approach (Campbell & Fiske, 1959). With regard to research question 2, results revealed that the internal structure of ASC and SE could be validly assessed. However, the assessment of psychology students" SE should follow a task-specific measurement strategy. Results of research question 3 further showed that both constructs of psychology students" competence-related self-perceptions were positively correlated to achievement in undergraduate psychology courses if predictor (ASC, SE) corresponded to measurement specificity of the criterion (achievement). Overall, ASC provided substantially stronger relations to achievement compared to SE. Moreover, there was evidence for negative paths (contrast effects) from achievement in one psychological domain on ASC of another psychological domain as postulated by the internal/external frame of reference (I/E) model (Marsh, 1986). Finally, building on research questions 1 to 3 (structure, measurement, and correlates of ASC and SE), psychology students" ASC and SE were be differentiated on an empirical level (research question 4). Implications for future research practices are discussed. Furthermore, practical implications for enhancing ASC and SE in higher education are proposed to support academic achievement and the career development of psychology students.