Positive interpersonal relationships hinge on individuals’ competence in regulating others’ emotions as well as their own. Nevertheless, little is known about the relationship between emotional competence and specific interpersonal behaviors. In particular, it is unclear which situations require emotional competence for extrinsic emotion regulation and whether emotionally competent individuals actually attempt to regulate others’ emotions. To clarify these issues, the current investigation examined the relationship between emotional competence and extrinsic emotion regulation directed toward an ostracized person. The results of Study 1 (N = 39) indicated that interpersonal emotional competence (competence related to others’ emotions) was positively associated with participants’ efforts to relieve the ostracized person’s sadness. In Study 2 (N = 120), this relationship was moderated by the ostracized person’s emotional expression. In particular, participants with high interpersonal emotional competence were more likely to attempt to regulate the sadness of ostracized individuals who expressed neutral affect. In contrast, when the ostracized person expressed sadness, there were no significant relationships between high or low interpersonal emotional competence and extrinsic emotion regulation behavior. These results offer novel insight into how emotionally competent individuals use their competence to benefit others.