Organizational learning is an important means for improving performance. Learning is a process, that is, often relational in the sense of relying on interactions between people to determine what needs improving and how to do it. This study addresses the question of how the quality of work relationships facilitates learning behaviours in organizations through the ways it contributes to psychological safety. Data collected from 212 part-time students who hold full-time jobs in organizations operating in a wide variety of industries show that capacities of high-quality relationships (measured at time 1) are positively associated with psychological safety, which, in turn, are related to higher levels of learning behaviours (measured at time 2). The results also show that experiences of high-quality relationships (measured at time 1) are both directly and indirectly (through psychological safety) associated with learning behaviours (measured at time 2). These findings shed light on the importance of quality relationships in the workplace for cultivating and developing perceptions of psychological safety and ultimately learning behaviours in organizations.