The approximate number system (ANS) is assumingly related to mathematical learning but evidence supporting this assumption is mixed. The inconsistent findings might be attributed to the fact that different measures have been used to assess the ANS and mathematical skills. Moreover, associations between the performance on a measure of the ANS and mathematical skills may be discontinuous, i.e., stronger for children with lower math scores than for children with higher math scores, and may change with age. The aim of the present study was to examine the development of the ANS and arithmetic skills in elementary school children and to investigate how the relationship between the ANS and arithmetic skills develops. Individual markers of children's ANS (internal Weber fractions and mean reaction times in a non-symbolic numerical comparison task) and addition skills were assessed in their first year of school and 1 year later. Children showed improvements in addition performance and in the internal Weber fractions, whereas mean reaction times in the non-symbolic numerical comparison task did not change significantly. While children's addition performance was associated with the internal Weber fractions in the first year, it was associated with mean reaction times in the non-symbolic numerical comparison task in the second year. These associations were not found to be discontinuous and could not be explained by individual differences in reasoning, processing speed, or inhibitory control. The present study extends previous findings by demonstrating that addition performance is associated with different markers of the ANS in the course of development.