Introduction: This study explored the relationship between person–job fit and safety behavior, as well as the mediating role played by psychological safety, from the perspective of social cognitive theory and person–environment fit theory. Method: A total of 800 employees from petroleum enterprises were recruited, with cluster random sampling used to collect data in two stages. Results: The results showed that employees’ safety behavior is higher under the condition of ‘‘high person–job fit—high person–organization fit” than under that of ‘‘low person–job fit—low person–organization fit.” In other words, the more congruent the level of person–job fit and person–organization fit for a given employee, the higher their level of safety behavior. Practical Applications: Psychological safety plays a mediating role between the congruence of both person–job fit and person–organization fit and employees’ safety behavior.