This study examines the relevance of interpersonal relationships in the work environment, focusing specifically on analyzing associations between positive relational management, which refers to the use of relational resources that enable adaptation to the workplace, and key organizational variables such as flourishing, individual-directed organizational citizenship behaviors (OCBis), and life satisfaction. Given the importance of this topic, a structural model is required for the possible relationship between positive relational management and other organizational variables relevant to occupational well-being. As a preliminary step, the Positive Relational Management Scale (PRMS) was analyzed and validated in a sample of 348 Spanish workers. The results revealed that the overall model has a good fit, with reliable and valid construct measures. Moreover, the three-dimensional structure of the model was confirmed, although gender invariance was not satisfied. In conclusion, the results confirm the simple mediation hypothesis, in which flourishing mediates the relationship between positive relational management and life satisfaction. In contrast, multiple mediations between the variables could not be confirmed. This study highlights the importance of interpersonal relationships for employee well-being in the workplace.