Relational goals newly added to the teachers’ goal orientation framework have been identified as one of the central features of effective teaching. However, little research has taken such goals into account, specifically in higher education contexts. Concerning the association between self-efficacy and goal orientations, this study was undertaken to investigate the predictive power of instructors’ relational goals over teaching-related outcomes with teaching self-efficacy as a mediator. Three hundred thirty-eight Iranian EFL university instructors participated in the study. Their relational goals and teaching-related cognitive, affective, and behavioral outcomes were assessed through four scales (Instructors’ Achievement Goals for Teaching, Attitudes towards Help-Seeking, Positive Affect, and SEEQ (Students’ Evaluations of Educational Quality) Self-Reported Teaching Quality). Through a Structural Equation Modeling method, the proposed model was tested. The results confirmed the mediating effect of teaching self-efficacy on the relationship between instructors’ relational goals and their teaching-related outcomes. Relational goal-oriented instructors with teaching self-efficacy viewed help-seeking (cognitive outcomes) as a beneficial performance rather than a threat. Regarding their positive affect (affective outcomes), the results indicated instructors’ great enthusiasm for more effective teaching. Considering instructors’ self-reported teaching quality (behavioral outcomes), their engagement and commitment in teaching were shown. In conclusion, the results emphasized the importance of instructors’ relational goals in establishing high-quality learning and teaching environments.