Symbolic numbers contain information about their relative numerical cardinal magnitude (e.g., 2 < 3) and ordinal placement in the count-list (e.g., 1, 2, 3). Previous research has primarily investigated magnitude discrimination skills and their predictive capacity for math achievement, whereas numerical ordering has been less systematically explored. At approximately 10-12 years of age, numerical order processing skills have been observed to surpass cardinal magnitude discrimination skills as the key predictor of arithmetic ability. The neurocognitive mechanisms underlying this shift remain unclear. To this end, we investigated children’s (ages 10-12) neural correlates of numerical order and magnitude discrimination, as well as task-based functional connectomes and their predictive capacity for numeracy-related behavioral outcomes. Results indicated that number discrimination uniquely relied on bilateral temporoparietal correlates, whereas order processing recruited the bilateral IPS, cerebellum, and left premotor cortex. Connectome-based models were not cross-predictive for numerical order and magnitude, suggesting two dissociable mechanisms jointly supported by visuospatial working memory. Neural correlates of learning and memory were predictive of age and arithmetic ability, only for the ordinal task-connectome, indicating that the numerical order mechanism may undergo a developmental shift, dissociating it from mechanisms supporting cardinal number processing.