<p>Previous studies on alleviating students’ learning anxiety have mostly focused on the home-school perspective and explored the role played by parents or teachers. However, less attention was paid to the important function of nature for children’s learning and the mechanism underlying it was still underdeveloped. To explore how and for whom nature connectedness related to learning anxiety in primary school students, this study employed the Disposition to Connect to Nature scale, Learning Motivation Scale, and Diagnostic Test of Mental Health to assess 470 primary school students (mean age 9.91 ± 0.70 years, 221 males) in three follow-up tests for one year. The results showed that when controlling for covariates, (1) T1 (Time 1) nature connectedness was longitudinally and negatively associated with T3 (Time 3) learning anxiety; (2) T2 (Time 2) learning motivation partially mediated the association between T1 nature connectedness and T3 learning anxiety; and (3) the association between T2 learning motivation and T3 learning anxiety was moderated by gender, in which higher learning motivation was associated with lower learning anxiety in girls, while this relationship was not significant in boys. These findings suggest implications for leveraging nature connectedness as a means to reduce learning anxiety and enhance mental well-being among primary school students.</p>