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Parental Reflective Functioning (PRF) describes parents’ capacity to reflect on their child’s and their own mental states in the context of their relationship with the child. This study investigated the moderating role of PRF in the relationship between children’s temperament and internalizing and externalizing problems among 357 Iranian mothers (M = 37.34, SD = 5.29) and their children (M = 7.26, SD = 2.96; 48.7% girls). The instruments were the Children’s Behavior Questionnaire, Parental Reflective Functioning Questionnaire, and Child Behavior Checklist. The results showed that effortful control was negatively correlated with pre-mentalizing, internalizing, and externalizing problems and positively correlated with certainty and interest and curiosity. Negative affectivity was positively associated with pre-mentalizing, internalizing, and externalizing problems. Moreover, surgency/extraversion showed a negative correlation only with internalizing problems. Findings of regression analyses revealed that pre-mentalizing moderated the relationship between effortful control and internalizing and externalizing problems, and between negative affectivity and externalizing. In addition, certainty moderated the relationship between surgency/extraversion and internalizing. However, the interest and curiosity subscale indicated no moderating effect on the relationship between children’s temperament and emotional and behavioral problems. These findings highlight the significance of the role of PRF and a child’s temperament in emotional and behavioral difficulties.