In accordance with the emotional priming hypothesis, emotions seem to modulate pain perception and pain tolerance thresholds. To further evaluate this association, event-related brain potentials (ERPs) elicited by painful and nonpainful electrical stimuli during processing of positive, neutral, and negative valenced pictures were recorded from 30 healthy volunteers. Valence of pictures affected pain ratings and the N150 elicited by painful stimuli, with lowest amplitudes for positive pictures and highest amplitudes for negative pictures. The P260 elicited by painful and nonpainful stimuli was modulated by arousal with reduced amplitudes with arousing (positive or negative) compared to neutral pictures. N150 amplitudes varying with picture valence seem to reflect an affective modulation of pain perception whereas P260 amplitudes varying with picture arousal rather reflect non-pain-specific attentional processes.