The present study was aimed at identifying potential behavioral and neural correlates of Emotional Intelligence (EI) by using scalp-recorded Event-Related Potentials (ERPs). EI levels were defined according to both self-report questionnaire and a performance-based ability test. We identified ERP correlates of emotional processing by using a visual-emotional oddball paradigm, in which subjects were confronted with one frequent standard stimulus (a neutral face) and two deviant stimuli (a happy and an angry face). The effects of these faces were then compared across groups with low and high EI levels. The ERP results indicate that participants with high EI exhibited significantly greater mean amplitudes of the P1, P2, N2, and P3 ERP components in response to emotional and neutral faces, at frontal, posterior-parietal and occipital scalp locations. P1, P2 and N2 are considered indexes of attention-related processes and have been associated with early attention to emotional stimuli. The later P3 component has been thought to reflect more elaborative, top-down, emotional information processing including emotional evaluation and memory encoding and formation. These results may suggest greater recruitment of resources to process all emotional and non-emotional faces at early and late processing stages among individuals with higher EI. The present study underscores the usefulness of ERP methodology as a sensitive measure for the study of emotional stimuli processing in the research field of EI.