Phosphorus (P) is a major plant nutrient, however, its availability in volcanic ash soils is presumed to be small, due to its specific sorption on short‐range order minerals. We analyzed distinct P fractions in volcanic ash soils of different age (60 to > 100,000 y BP) under pine forests in Central Mexico to investigate their changes along a chronosequence of Regosols, Andosols, and Lixisols, and to evaluate if P availability limits tree growth at any particular stage. Top soil and subsoil samples were first analyzed by the Tiessen and Moir method, which failed to extract exhaustively “organic” and “occluded P”, and “P associated with apatite”. Therefore, we modified the fractionation scheme by including a “recalcitrant organic P” fraction obtained from the difference between P determined in air‐dried subsamples and subsamples burned at 300°C; P adsorbed to short‐range order minerals was assessed in an extraction with NH4‐oxalate, and P in primary minerals by subtracting the sum of all other fractions from total P contents determined by XRF. This we did after discovering that primary P occurred in the form of fluorapatite included in plagioclase, volcanic glass or olivine. We also measured P contents in pine needles and related these with the “mobile soil P” fractions. The results show that “organic P” reaches maximum contents in 10,000‐y old soil, as does P associated with short‐range order minerals, while P occluded into crystalline oxides increases constantly over time. After 100,000 y, 31% of total P still remains in the form of primary P in A horizons. “Mobile P” was constant > 40 mg kg−1 in Regosols and Andosols and related positively with foliar P contents, which were within adequate nutritional ranges. Only in Lixisols small “mobile P” concentrations in soil correspond with inadequate P contents in pine needles.