The paper presents the structure and algorithm of psychodiagnostic studies in Olympic sports on the basis of the methodological approach. The order of structural components is determined as a basis for developing implementation algorithm for the methodology. The basic forms of manifestations of athlete’s mentality and their relationship are examined. Using the assessment results of Ukrainian national team members specialized in cyclic, complex coordination, team or combat sports during preparation for the main competition of the year, the peculiarities and distinctions of their psychological profiles are identified to demonstrate the usability of implementation algorithm for the methodology of psychodiagnostic studies in Olympic sports. Individual and group characteristics of the type of temperament were studied, as well as the percentage distribution of different types of temperament in various sports. The indicators of the levels of psychological and physiological stress and of the peculiarities of perception, along with the gender characteristics were analyzed as fundamental psychological determinants of athlete’s personality. The key psychological factors of predisposition of athletes to a certain type of physical activity are investigated. The ways are suggested to improve the algorithm of psychodiagnostic testing and development of different aspects of athlete’s sporting potential.