A variety of theoretical perspectives describe the crucial behavioral roles of motivation and emotion, but how these interact with perceptions of social contexts and behaviors is less well understood. This study examined whether autonomous motivation mediated the relationship between perceived autonomy support and behavioral engagement in physical education and whether this mediating process was moderated by positive emotion. A sample of 592 Korean middle-school students (304 boys, 288 girls; M age = 14.0 yr., SD = 0.8) completed questionnaires. Autonomous motivation partially mediated the positive association between perceived autonomy support and behavioral engagement. Positive emotion moderated the relationship between autonomous motivation and behavioral engagement. This indirect link was stronger as positive emotion increased. These findings suggest the importance of integrating emotion into motivational processes to understand how and when perceived autonomy support is associated with behavioral engagement in physical education.