This study analyzed the cognitive functioning underlying arithmetical difficulties and explored the predictors of arithmetic achievement in the last three grades of Spanish Primary Education. For this purpose, a group of 165 students was selected and divided into three groups of arithmetic competence: Mathematical Learning Disability group (MLD, n = 27), Low Achieving group (LA, n = 39), and Typical Achieving group (TA, n = 99). Students were assessed in domain-general abilities (working memory and PASS cognitive processes), and numerical competence (counting and number processing) during the last two months of the academic year. Performance of children from the MLD group was significantly poorer than that of the LA group in writing dictated Arabic numbers (d = –0.88), reading written verbal numbers (d = –0.84), transcoding written verbal numbers to Arabic numbers (–0.75) and comprehension of place value (d = –0.69), as well as in simultaneous (d = –0.62) and successive (d = –0.59) coding. In addition, a specific developmental sequence was observed in both groups, the implications of which are discussed. Hierarchical regression analysis revealed simultaneous coding (β = .47, t(155) = 6.18, p < .001) and number processing (β = .23, t(155) = 3.07, p < .01) as specific predictors of arithmetical performance.