Mathematics anxiety has been associated to performance in school mathematics. The association between math anxiety and psychosocial competencies as well as their specific contribution to explain school mathematics performance are still unclear. In the present study, the impact of sociodemographic factors, psychosocial competencies, and math anxiety on mathematics and spelling performance was examined in school children with and without mathematics difficulties. The specific contributions of psychosocial competencies (i.e., general anxiety and attentional deficits with hyperactivity) and math anxiety (i.e., self-assessment in mathematics) to school mathematics performance were found to be statistically independent from each other. Moreover, psychosocial competencies—but not math anxiety—were related also to spelling performance. These results suggest that psychosocial competencies are more related to general mechanisms of emotional regulation and emotional response towards academic performance, while mathematics anxiety is related to the specific cognitive aspect of self-assessment in mathematics.