Several ERP studies have shown an orienting complex, the N2/P3a, associated to the detection of stimulus novelty. Its role consists in preparing the organism to process and react to biologically prepotent stimuli. Whether this N2/P3a: (1) could be obtained with complex visual stimuli, such as with emotional facial expressions; and (2) could take part in a complex discrimination process has yet to be determined. To investigate this issue, event-related potentials were recorded in response to repetitions of a particular facial expression (e.g. sadness) and in response to two different deviant (rare) stimuli, one depicting the same emotion as the frequent stimulus, while the other depicted a different facial expression (e.g. fear). As expected, deviant stimuli evoked an N2/P3a complex of larger amplitude than frequent stimuli. But more interestingly, when the deviant stimulus depicted the same emotion as the frequent stimulus the N2/P3a was delayed compared to the response elicited by the different-emotion deviant. The N2/P3a was thus implicated in the detection of physical facial changes, with a higher sensitivity to changes related to a new different emotional content, perhaps leading to faster adaptive reactions.