Acquisition of numerical knowledge and understanding of numerical information are crucial for coping with the changing demands of our digital society. In this study, we assessed arithmetic learning in older and younger individuals in a training experiment including brain imaging. In particular, we assessed age-related effects of training intensity, prior arithmetic competence, and neuropsychological variables on the acquisition of new arithmetic knowledge and on the transfer to new, unknown problems. Effects were assessed immediately after training and after 3 months. Behavioural results showed higher training effects for younger individuals than for older individuals and significantly better performance after 90 problem repetitions than after 30 repetitions in both age groups. A correlation analysis indicated that older adults with lower memory and executive functions at baseline could profit more from intensive training. Similarly, training effects in the younger group were higher for those individuals who had lower arithmetic competence and executive functions prior to intervention. In younger adults, successful transfer was associated with higher executive functions. Memory and set-shifting emerged as significant predictors of training effects in the older group. For the younger group, prior arithmetic competence was a significant predictor of training effects, while cognitive flexibility was a predictor of transfer effects. After training, a subgroup of participants underwent an MRI assessment. A voxel-based morphometry analysis showed a significant interaction between training effects and grey matter volume of the right middle temporal gyrus extending to the angular gyrus for the younger group relative to the older group. The reverse contrast (older group vs. younger group) did not yield any significant results. These results suggest that improvements in arithmetic competence are supported by temporo-parietal areas in the right hemisphere in younger participants, while learning in older people might be more widespread. Overall, our study indicates that arithmetic learning depends on the training intensity as well as on person-related factors including individual age, arithmetic competence before training, memory, and executive functions. In conclusion, we suggest that major progress can be also achieved by older participants, but that interventions have to take into account individual variables in order to provide maximal benefit.