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Social ties are crucial for humans. Disruption of ties through social exclusion has a marked effect on our thoughts and feelings; however, such effects can be tempered by broader social network resources. Here, we use fMRI data acquired from 80 male adolescents to investigate how social exclusion modulates functional connectivity within and across brain networks involved in social pain and understanding the mental states of others (i.e., mentalizing). Furthermore, using objectively logged friendship network data, we examine how individual variability in brain reactivity to social exclusion relates to the density of participants’ friendship networks, an important aspect of social network structure. We find increased connectivity within a set of regions previously identified as a mentalizing system during exclusion relative to inclusion. These results are consistent across the regions of interest as well as a whole-brain …