Phosphorus (P) limitation is expected to increase due to nitrogen (N)-induced terrestrial eutrophication, although most soils contain large P pools immobilized in minerals (P_i) and organic matter (P_o). Here we assessed whether transformations of these P pools can increase plant available pools alleviating P limitation under enhanced N availability. The mechanisms underlying these possible transformations were explored by combining results from a 10-year field N-addition experiment and a 3700-km transect covering wide ranges in soil pH, soil N, aridity, leaching, and weathering that can affect soil P status in grasslands. Nitrogen addition promoted dissolution of immobile P_i (mainly Ca-bound recalcitrant P) to more available forms of P_i (including Al- and Fe-bound P fractions and Olsen P) by decreasing soil pH from 7.6 to 4.7, but did not affect P_o. Soil total P declined by 10% from 385±6.8 to 346±9.5 mg kg^-1, while available-P increased by 546% from 3.5±0.3 to 22.6±2.4 mg kg^-1 after 10-year N addition, associated with an increase in P_i mobilization, plant uptake, and leaching. Similar to the N-addition experiment, the drop in soil pH from 7.5 to 5.6 and increase in soil N concentration along the grassland transect were associated with an increased ratio between relatively mobile P_i and immobile P_i. Our results provide a new mechanistic understanding of the important role of soil P_i mobilization in maintaining plant P supply and accelerating biogeochemical P cycles under anthropogenic N enrichment. This mobilization process temporarily buffers ecosystem P-limitation or even causes P eutrophication but will extensively deplete soil P pools in the long run.