Social exclusion is known to cause alterations in neural activity and perceptions of social distress. However, previous research is largely limited to examining social interactions as a unitary phenomenon without investigating adjustments in neural and attentional processes that occur during social interactions. To address this limitation, we examined neural activity on a trial-by-trial basis during different social interactions. Our results show conflict monitoring neural alarm activation, indexed by the N2, in response to specific exclusionary events; even during interactions that are inclusionary overall and in the absence of self-reported feelings of social pain. Furthermore, we show enhanced attentional activation to exclusionary events, indexed by the P3b, during exclusionary, compared with inclusionary, interactions, and this P3b activation was associated with self-reported social distress following prolonged social exclusion. Finally, both the N2 and P3b showed larger amplitudes in the earlier stages of exclusion compared with later stages, suggesting heightened early sensitivity for both components. Together, these findings provide novel insights into the dynamic neural and perceptual processes of exclusion that exist during social interactions and the relationship between discrete events within interactions and the more general contexts of the social interactions.