This chapter examines the role of interpersonal neural synchronization (INS) in effective teaching within educational settings. Utilizing hyperscanning techniques, recent research has revealed that INS, the temporal coupling of brain activity between individuals, serves as a neural marker of successful teacher-student interaction. This chapter discusses how both time-aligned INS, associated with shared external stimuli, and time-lagged INS, reflecting interpersonal cognitive processes like prediction, contribute to learning outcomes. It explores the neurocognitive mechanisms underlying INS, including its evolutionary basis in face-to-face communication and the role of selective attention in multi-individual contexts. Furthermore, this chapter reviews studies demonstrating the impact of interaction modes and teacher-student relationships on INS and learning. While highlighting the potential of INS as a valuable tool in educational neuroscience, this chapter also acknowledges the need for further research addressing causal relationships, practical applications for pedagogy, and considerations of individual differences in diverse learning environments.