The personality trait of extraversion has been linked to the network of brain systems controlling sensitivity to cues of reward and generating approach behavior in response, but little is known about whether extraverts' neural circuits are especially sensitive to social stimuli, given their preference for social engagement. Utilizing event-related potential (ERP) methodology, this study demonstrates that variation on the extraversion dimension is associated with the extent to which social stimuli evoke enhanced allocation of attention. Specifically, higher scores on extraversion were found to be associated with higher amplitudes of the P300 component of the ERPs elicited by human faces. This finding suggests that social stimuli carry enhanced motivational significance for individuals characterized by high extraversion, and that individual differences in personality are related to meaningful individual differences in neural responses to social stimuli.