Introduction. A number of researchers have reported the influence of metacognition and self-regulation on learning and academic performance. However, to date there has been little agreement on how these processes are related to each other. This study is aimed at identifying the relationship between metacognition and mental self-regulation of learning, as well as comparing the components of metacognitive awareness among students with different levels of mental self-regulation. Materials and Methods. A theoretical framework of this study included J. Flavell and A. Brown's Metacognition Theory; Konopkin's Structural-Functional Approach to Studying Conscious Self-Regulation and B. Zimmerman's Self-Regulated Learning Theory. The study used the following psychological testing techniques: (a) V. Morosanova's Style of Behaviour self-regulation questionnaire, (b) G. Schraw & R. Dennison's Metacognitive Awareness Inventory (short version) adapted by Perikova and Byzova, (c) E. Y. Mandrikova's Self-regulation questionnaire, (d) D. V. Lyusin's Emotional intelligence inventory, (e) D. A. Leontiev's Differential reflexivity diagnostic. The sample consisted of 186 students of St. Petersburg State University aged 19,51±1,39 years. Results. The results indicate a wide range of relationships between mental self-regulation and metacognitive, cognitive, motivational and emotional components. Self-regulation is primarily linked with metacognitive processes of control and regulation of cognition, as well as cognition management. Metacognitive awareness of general and individual patterns, cognitive abilities and strategies are included in the process of self-regulation to a lesser extent. However, the results of factor analysis and regression analysis indicate that metacognition components did not affect self-regulation. Analysis of the variance confirmed that individuals with a low level of self-regulation demonstrate significantly less pronounced metacognitive, motivational and emotional components. Conclusions. The study demonstrates the systemic nature of the relationship between mental self-regulation and metacognitive components, as well as cognitive, motivational and emotional components.