Individual differences in face memory abilities have been shown to be related to individual differences in brain activity. The present study investigated brain-behavior relationships for the N250 component in event-related brain potentials, which is taken as a neural sign of face familiarity. We used a task in which a designated, typical target face and several (high- and low-distinctive) nontarget faces had to be distinguished during multiple presentations across a session. Separately, face memory/recognition abilities were measured with easy versus difficult tasks. We replicated an increase of the N250 amplitude to the target face across the session and observed a similar increase for the non-target faces, indicating the build-up of memory representations also for these faces. On the interindividual level, larger across-session N250 amplitude increases to low-distinctive non-target faces were related to faster face recognition as measured in an easy task. These findings extend the present knowledge about brain-behavior relationships in face memory/recognition and indicate that an advantage in non-intentional encoding of low-distinctive non-target faces into memory goes along with the swift recognition of explicitly learned faces.