It is widely accepted that the human brain is remarkably adaptive not only in child development, but also during adulthood. Aim of this work is to offer an overview and a systematic analysis of neuroimaging studies on the acquisition of arithmetic expertise. In normally developing children and adults, the gain of arithmetic competence is reflected by a shift of activation from frontal brain areas to parietal areas relevant for arithmetic processing. A shift of activation is also observed within the parietal lobe from the intraparietal sulci to the left angular gyrus. Increases in angular gyrus activation with gaining of expertise have also been documented in other cognitive domains. It appears that the left angular gyrus activation is modulated by inter-individual differences in arithmetic performance. The comparison of normal individuals with exceptionally performing individuals (e.g., calculating prodigies) suggests that the experts' arithmetic proficiency relies on a more extended activation network than the network found in non-experts. In expert individuals with long-lasting, extensive mathematical training, specific structural brain modifications are also evident.