Neuroimaging findings in adults suggest exact and approximate number processing relying on distinct neural circuits. In the present study we are investigating whether this cortical specialization is already established in 9- and 12-year-old children. Using fMRI, brain activation was measured in 10 third- and 10 sixth-grade school children and 20 adults during trials of symbolic approximate (AP) and exact (EX) calculation, as well as non-symbolic magnitude comparison (MC) of objects. Children activated similar networks like adults, denoting an availability and a similar spatial extent of specified networks as early as third grade. However, brain areas related to number processing become further specialized with schooling. Children showed weaker activation in the intraparietal sulcus during all three tasks, in the left inferior frontal gyrus during EX and in occipital areas during MC. In contrast, activation in the anterior cingulate gyrus, a region associated with attentional effort and working memory load, was enhanced in children. Moreover, children revealed reduced or absent deactivation of regions involved in the so-called default network during symbolic calculation, suggesting a rather general developmental effect. No difference in brain activation patterns between AP and EX was found. Behavioral results indicated major differences between children and adults in AP and EX, but not in MC. Reaction time and accuracy rate were not correlated to brain activation in regions showing developmental changes suggesting rather effects of development than performance differences between children and adults. In conclusion, increasing expertise with age may lead to more automated processing of mental arithmetic, which is reflected by improved performance and by increased brain activation in regions related to number processing and decreased activation in supporting areas.