Effective natural resource management (NRM) often depends on collaboration through formal and informal relationships. Social network analysis (SNA) provides a framework for studying social relationships; however, a deeper understanding of the nature of these relationships is often missing. By integrating multiple analytical methods (including SNA, evidence ratings, and perception matrices), we were able to investigate the nature of relationships in NRM social networks across five service types (e.g., technical advice, on-ground support) in our case study region, Daly catchment Australia. Only one service type was rated as highly associated with free choice in establishing relationships: technical advice/knowledge. Beneficial characteristics of NRM organizations, such as collaborative and transparent, were associated with the presence of freely chosen relationships between organizations. Our results suggest a need to improve our understanding of organizational roles and characteristics, in particular for use in applied NRM contexts, such as network weaving or disseminating information.