This study investigated the different effects of teacher-student rapport on urban and rural students' math learning via mathematics self-efficacy and mathematics anxiety in China. The participants were 8145 urban and rural fourth graders (mean age = 10 years old) in a central city of China. The findings indicated that (a) compared with rural students, urban students reported significantly higher mean scores for teacher-student rapport, mathematics self-efficacy, and mathematical academic outcome, and significantly lower mean scores for mathematics anxiety; (b) students perceived teacher-student rapport in urban and rural schools had a substantial effect on students' mathematical academic outcome through increasing students' mathematics self-efficacy and alleviating students' mathematics anxiety; and (c) teacher-student rapport in rural schools majorly increased their students' mathematical academic outcome via boosting rural students' mathematics self-efficacy rather than reducing their mathematical anxiety, which is significantly different from that for urban students. Implications and future directions are elaborated.