AbstractPhosphorus inputs must be estimated accurately to optimize the economic return to farmers and minimize P loss from soils to surface waters. Currently, P recommendations are based on the diagnosis of field crop responses by chemically extracted soil P. However, the inability of chemical extraction to characterize plant‐available P limits the reliability of these recommendations. Major sources of P mobilized by plant roots include P ions in solution and those from soil constituents, which replenish and buffer solution. A mechanistic evaluation of soil P supply should therefore be based on the description of P ion transfer between soil constituents and solution. Sorption, desorption, electro‐ultrafiltration (EUF), and isotopic exchange studies show that an adequate modeling of this quantity [Q(CP,t)] of P ions must account for both the concentration of P ions in soil solution (Cp) and time (t). In one long‐term field experiment, the Q(CP,t) description was not affected by crop rotation and mineral fertilization histories; therefore, Q(CP,t) changes are fully explained by CP changes. In two field experiments, CP changes were linearly correlated with the cumulative P budget, inputs, and outputs over years. In three field experiments, the soil type effect on the relative maize (Zea mays L.) response curve was taken into account using the ability of soil P to replenish solution P for 1 d. The residual variance of this diagnosis is halved compared to Olsen's extraction. Although more information is necessary, accuracy is improved when soil testing is based on mobility of P ions.