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We examined the associations among teacher-student relationship quality (TSRQ), emotional engagement, feelings of belonging, and classroom goal structures among a sample of 306 middle school students in Greece. Our results indicated that students nested within classrooms varied in their perceptions of their TSRQ and in their belonging and emotional engagement. In addition, we found that classroom goal structures have both direct and indirect (through TSRQ) associations with belonging and emotional engagement. We found evidence of significant mediation for the relationship between classroom mastery goal structures and emotional engagement through positive TSRQ. These results shed light on one mechanism through which classroom goal structures may influence students’ affective experience in classrooms. The implications for research and practice are discussed.