While the left angular gyrus (lAG) has been repeatedly implicated in mental arithmetic, its precise functional role has not been established. On the one hand, it has been speculated that the lAG is involved in task-specific processes. On the other hand, the observation of relative deactivation during arithmetic has led to the contention that differential lAG activation reflects task-unrelated difficulty effects associated with the default mode network (DMN). Using functional magnetic resonance imaging, we investigated the neural correlates of the associative confusion effect that allowed us to dissociate effects of task difficulty and task-related arithmetic processes on lAG activation. The associative confusion effect is characterized by poorer performance while verifying addition and multiplication equations whose solutions are associated with the other operation (confusion equations: e.g., “9 × 6 = 15”) compared with solutions unrelated to both operations (non-confusion equations: e.g., “9 × 6 = 52”). Comparing these two conditions revealed higher activation of the anterior lAG (areas PGa, PFm, and PF) and the left dorsolateral prefrontal cortex for the confusion problems. This effect displayed only slight anatomical overlap with the well-established reverse problem-size effect (small minus large problems) and task-related deactivation in the parietal cortex. The finding of greater lAG activity (less deactivation) in the more difficult task condition is inconsistent with the hypothesis that lAG activation during mental arithmetic reflects task difficulty related modulations of the DMN. Instead, the present findings provide further support for the symbol-referent mapping hypothesis, suggesting that the lAG mediates the automatic mapping of arithmetic problems onto solutions stored in memory. Hum Brain Mapp, 2013. © 2011 Wiley Periodicals, Inc.