Do individual differences in the brain mechanisms for arithmetic underlie variability in high school mathematical competence? Using functional magnetic resonance imaging, we correlated brain responses to single digit calculation with standard scores on the Preliminary Scholastic Aptitude Test (PSAT) math subtest in high school seniors. PSAT math scores, while controlling for PSAT Critical Reading scores, correlated positively with calculation activation in the left supramarginal gyrus and bilateral anterior cingulate cortex, brain regions known to be engaged during arithmetic fact retrieval. At the same time, greater activation in the right intraparietal sulcus during calculation, a region established to be involved in numerical quantity processing, was related to lower PSAT math scores. These data reveal that the relative engagement of brain mechanisms associated with procedural versus memory-based calculation of single-digit arithmetic problems is related to high school level mathematical competence, highlighting the fundamental role that mental arithmetic fluency plays in the acquisition of higher-level mathematical competence.