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Phosphorus (P) is an essential nutrient for sustaining life and agricultural production. Transformation of readily available P into forms that are unavailable to plants adds costs to P replenishment, which eventually translates into lower agronomic benefits and potential loss of soil P into runoff may degrade water quality. Therefore, understanding the sources and pathways of the formation of residual P pools in soils is useful information needed for the development of any technological or management efforts to minimize or inhibit the formation of such P pool and thus maximize availability to plants. In this research, we paired phosphate oxygen isotope ratios (δ18OP) with solid-state 31P NMR and quantitative XRD techniques along with general soil chemistry methods to identify the precipitation pathways of acid-extracted inorganic P (Pi) pools in an agricultural soil. Based on the comparison of isotope values of 0.5 mol L−1 NaOH-Pi, 1 mol L−1 HCl-Pi, and 10 mol L−1 HNO3-Pi pools and correlations of associated elements (Ca, Fe, and Al) in these pools, the HNO3-Pi pool appears most likely to be transformed from the NaOH-Pi pool. A narrow range of isotope values of acid-Pi pools in shallow (tilling depth) and below (where physical mixing is absent) is intriguing but likely suggests leaching of particle-bound P in deeper soils. Overall, these findings provide an improved understanding of the sources, transport, and transformation of acid-Pi pools in agricultural soils and further insights into the buildup of legacy P in soils.