Psychological inflexibility has been found to moderate psychological distress following perceived ostracism. Two component processes of psychological inflexibility, experiential avoidance and cognitive fusion, are considered key in exacerbating general emotional distress. The present study (n = 286) examined whether both experiential avoidance and cognitive fusion moderate distress from perceived ostracism or whether one of these processes alone underpins the moderation effect of psychological inflexibility. In a structural equation model analysis, when accounting for both factors, experiential avoidance moderated distress from perceived ostracism alone. Thus, it seems that experiential avoidance is a key driver underlying emotional regulation of psychological distress in the context of perceived ostracism.