The current study sought to examine whether sibling relationship is significantly related to adolescents’ prosocial behavior and whether this relationship is mediated by moral disengagement. Further, we examined whether empathy moderates the direct and indirect relationships between sibling relationship and adolescents’ prosocial behavior. A total of 659 adolescents from Shanxi Province completed the questionnaires, regarding their experience with sibling relationship, prosocial behavior, empathy, moral disengagement. Results showed that adolescents with positive sibling relationship were likely to engage in prosocial behavior. Moral disengagement significantly mediated the relationship between sibling relationship and prosocial behavior. Furthermore, empathy moderated the indirect relationship between sibling relationships and adolescents’ prosocial behavior via moral disengagement.Specifically, the path from sibling relationship to moral disengagement became weakened when adolescents had high levels of empathy.