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Peers are present for most bullying episodes. Peers who witness bullying can play an important role in either stopping or perpetuating the behaviour. Defending can greatly benefit victimized peers. Empathy is strongly associated with defending. Yet, less is known about defenders' neural response to witnessing social distress, and how this response may relate to the link between empathy and defending. Forty-six first-year undergraduate students (M_age = 17.7; 37 women), with varied history of peer defending, underwent fMRI scanning while witnessing a depiction of social exclusion. Functional connectivity analysis was performed across brain regions that are involved in cognitive empathy, empathetic distress, and compassion. History of defending was positively associated with functional connectivity (Exclusion > Inclusion) between the left orbitofrontal cortex (OFC) - medial prefrontal cortex (MPFC), and right OFC - left and right amygdalae. Defending was negatively associated with functional connectivity between the left OFC - anterior cingulate cortex. The relationship between history of defending and empathy (specifically, empathetic perspective taking) was moderated by functional connectivity of the right OFC - left amygdala. These findings suggest that coactivation of brain regions involved in compassionate emotion regulation and empathetic distress play a role in the relationship between empathy and peer defending.