The nature of the mapping process that imbues number symbols with their numerical meaning—known as the “symbol-grounding process”—remains poorly understood and the topic of much debate. The aim of this study was to enhance insight into how the nonsymbolic–symbolic number mapping process and its neurocognitive correlates might differ between small (1–4; subitizing range) and larger (6–9) numerical ranges. Hereto, 22 young adults performed a learning task in which novel symbols acquired numerical meaning by mapping them onto nonsymbolic magnitudes presented as dot arrays (range 1–9). Learning-dependent changes in accuracy and RT provided evidence for successful novel symbol quantity mapping in the subitizing (1–4) range only. Corroborating these behavioral results, the number processing related P2p component was only modulated by the learning/mapping of symbols representing small numbers 1–4. The symbolic N1 amplitude increased with learning independent of symbolic numerical range but dependent on the set size of the preceding dot array; it only occurred when mapping on one to four item dot arrays that allow for quick retrieval of a numeric value, on the basis of which, with learning, one could predict the upcoming symbol causing perceptual expectancy violation when observing a different symbol. These combined results suggest that exact nonsymbolic–symbolic mapping is only successful for small quantities 1–4 from which one can readily extract cardinality. Furthermore, we suggest that the P2p reflects the processing stage of first access to or retrieval of numeric codes and might in future studies be used as a neural correlate of nonsymbolic–symbolic mapping/symbol learning.