Decoding pain in others is of high individual and social benefit in terms of harm avoidance and demands for accurate care and protection. The processing of facial expressions includes both specific neural activation and automatic congruent facial muscle reactions. While a considerable number of studies investigated the processing of emotional faces, few studies specifically focused on facial expressions of pain. Analyses of brain activity and facial responses elicited by the perception of facial pain expressions in contrast to other emotional expressions may unravel the processing specificities of pain-related information in healthy individuals and may contribute to explaining attentional biases in chronic pain patients. In the present study, 23 participants viewed short video clips of neutral, emotional (joy, fear), and painful facial expressions while affective ratings, event-related brain responses, and facial electromyography (Musculus corrugator supercilii, M. orbicularis oculi, M. zygomaticus major, M. levator labii) were recorded. An emotion recognition task indicated that participants accurately decoded all presented facial expressions. Electromyography analysis suggests a distinct pattern of facial response detected in response to happy faces only. However, emotion-modulated late positive potentials revealed a differential processing of pain expressions compared to the other facial expressions, including fear. Moreover, pain faces were rated as most negative and highly arousing. Results suggest a general processing bias in favor of pain expressions. Findings are discussed in light of attentional demands of pain-related information and communicative aspects of pain expressions.