Several recent reports suggest that the behavioral and cortical specificity of face processing may be influenced by experience. To test this hypothesis, behavioral and electrophysiological data were recorded from adults in response to human and monkey faces differing in familiarity and orientation. An analysis of event-related potential and behavioral data revealed differentiation across species, familiarity, and orientation. Behavioral measures were correlated with amplitude and latency measures for each factor of interest. These analyses revealed that accuracy was positively related to the amplitude of the vertex positive potential in the human face task but not in the monkey face task. These findings suggest that previous experience with different categories of faces modulates the link between behavioral and electrophysiological measures of face processing.