The impact of social rejection varies significantly across individuals, and can have dire consequences for interpersonal relationships. Research suggests that those higher in rejection sensitivity (RS) show a hypervigilance for socially-rejecting cues, though results have been mixed. Participants with Adult Rejection Sensitivity Questionnaire (A-RSQ) scores in the top and bottom third of the qualified recruited sample completed tasks probing attentional responses to neutral, disgusted, and contemptuous facial expressions. A novel adaptive staircasing task revealed a greater attentional bias toward contemptuous faces among higher-RS viewers relative to disgusted and neutral expressions, a pattern not seen among lower-RS viewers. Event-related potential measures revealed distinct responses to contemptuous faces among higher-RS viewers at early stages, followed by later enhancements to affectively-valenced faces. Our results show that higher-RS viewers process facial expressions distinctly from those lower in RS and suggest that contemptuous faces constitute a valid stimulus for isolating social rejection sensitivity effects.