Mathematical knowledge is constructed hierarchically from basic understanding of quantities and the symbols that denote them. Discrimination of numerical quantity in both symbolic and non-symbolic formats has been linked to mathematical problem-solving abilities. However, little is known of the extent to which overlap in quantity representations between symbolic and non-symbolic formats is related to individual differences in numerical problem solving and whether this relation changes with different stages of development and skill acquisition. Here we investigate the association between neural representational similarity (NRS) across symbolic and non-symbolic quantity discrimination and arithmetic problem-solving skills in early and late developmental stages: elementary school children (ages 7–10 years) and adolescents and young adults (AYA, ages 14–21 years). In children, cross-format NRS in distributed brain regions, including parietal and frontal cortices and the hippocampus, was positively correlated with arithmetic skills. In contrast, no brain region showed a significant association between cross-format NRS and arithmetic skills in the AYA group. Our findings suggest that the relationship between symbolic-non-symbolic NRS and arithmetic skills depends on developmental stage. Taken together, our study provides evidence for both mapping and estrangement hypotheses in the context of numerical problem solving, albeit over different cognitive developmental stages.