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How does the structure of relationships among program staff in a multi-organization STEM pipeline enrichment program contribute to its success? Existing explanations for success in short-term organizational collaborations grounded in volunteer efforts across multiple sectors is not well-understood, especially as it pertains to STEM-based organizations. Using mixed-method social network analysis methods, we examine the social structure and narratives related to relationships in a collaborative network of 42 STEM program staff surveyed in 2019-20. Results indicate a loosely hierarchical network backbone of relationships that is largely unrelated to demographic attributes, and that alongside social status, personal values related to achievement and power (self-enhancement) are in part responsible for the formation of relationships. Qualitative responses gathered during in-depth interviews help us to corroborate the roles of structurally important actors identified via name generator methods in the relational success of the organizational collaboration. A secondary methodological contribution is the quantification of the value of adding a network roster and final free recall above and beyond an initial free recall question, which recovers at least fourfold more relationships than free recall alone. Our findings contribute to ongoing conversations about how abstract value orientations may contribute to relationship formation within and across social groups.