AbstractSoil legacy phosphorus (P) represents a substantial secondary P resource to postpone the global P crisis. To fully utilize this P reserve, the transformation of legacy P speciation in a black soil with and without P fertilization for 27 years was investigated by chemical fractionation, molecular-level bulk (P K-edge X-ray absorption near-edge, XANES; solution ³¹P nuclear magnetic resonance) and microprobe (µ-X-ray fluorescence and µ-XANES) spectroscopy. Results from both fractionation and P bulk-XANES concordantly indicated that Ca₂-P [Ca(H₂PO₄)₂] acts as a reserve of labile P in response to soils with or without P fertilization. Cropping for 27 years depleted hydroxyapatite while enriched iron-bound P in soils irrespective of P application. Similar accumulation of soil organic P (P_o), probably due to root residue inputs, occurred in both soils with and without P fertilization; the accumulated P_o was present as orthophosphate diesters in soils with P fertilization more than in soils without P fertilization, suggesting that the release of labile P_o was triggered by soil P deficits. These results provide vital information for agronomically and environmentally sustainable P management by demonstrating the potential crop availability of legacy soil P, which could reduce future P fertilization.