Prior research shows that parental psychological flexibility can benefit children’s social adjustment, but its role in mitigating peer victimization remains unclear. This study addressed this gap by examining the potential mediating roles of executive function and social anxiety in the longitudinal relationship between parental psychological flexibility and peer victimization. The sample comprised 511 primary school students (grades 4–6; 46.58% girls; Mage = 9.34, SD = 1.10) and their parents, followed three waves across one year. Results showed that parental psychological flexibility was negatively correlated with low executive function, social anxiety, and peer victimization. Structural equation modeling revealed that parental psychological flexibility predicted lower peer victimization both directly and indirectly through two distinct pathways—social anxiety alone and a chained mediation link from executive function to social anxiety. These findings underscore the importance and key explanatory mechanisms of parental psychological flexibility in mitigating the risk of peer victimization among children and early adolescence, offering valuable insights for the development of prevention and intervention strategies.