The present study explored a model of the interplay between mother’s parental psychological flexibility of Chinese primary school students (grade 3–6) and self-reliance behaviors, as well as whether resilience mediates this association. Participants were N = 497 children attending three primary schools in Jiangsu Province (N = 240, Mage = 10.51 years, SD = 3.60; 47.6% boys) and two primary schools in Fujian Province (N = 257, Mage = 10.92 years, SD = 3.31; 45.3% boys), People’s Republic of China. Assessments were employed, with children rating their mother’s parental psychological flexibility, as well as their own resilience and self-reliance behaviors. Results indicated that there was a significant positive correlation between mother’s parental psychological flexibility of Chinese primary school students (grades 3–6), resilience, and self-reliance behaviors. Moreover, resilience played a complete mediating role between mother’s parental psychological flexibility and self-reliance behaviors; the mediating effect of goal focus and emotional control (two subfactors of resilience) between mother’s parental psychological flexibility and self-reliance behaviors was significant, while the mediating effect of positive thinking, family support, and interpersonal assistance (the other three subfactors of resilience) was insignificant. The findings understress the importance of considering the meaning and implication of mother’s parental psychological flexibility and resilience in Chinese culture.