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Developmental network (DN) theory advanced our understanding of mentoring by distinguishing between the content (e.g., career support) and the structural characteristics (e.g., effective size, density) of developmental mentoring networks. The current study aimed to test the influence of DN content and structure on undergraduate women’s longitudinal social integration into STEM fields. 235 undergraduate women in STEM disciplines at 10 universities completed surveys concerning their science identity, STEM graduate school applications, and DN characteristics over-time. Egocentric network analysis and longitudinal structural equation modeling reveal that DN career support and effective size predicted short-term identity; while DN density predicted long-term science identity and STEM graduate school applications. The implications of DN structures forming “sticky webs” that drive identity and persistence are discussed.