SUMMARYThe significance of exchangeable cations in the release of phosphorus by sequential extraction with water was evaluated in 11 acid (pH 5.0–6.3) New Zealand soils contrasting in P status and P retention. The release of P from Na‐saturated soil exceeded that from the original Ca‐dominated soils by up to four‐fold. Possible explanations for the larger P release in the Na system include: (i) desorption of P induced by increased surface negative potential associated with the exchange of Na for Ca/Mg, and/or (ii) accelerated dissolution of Ca phosphate compounds or complexes resulting from the creation of a sink for Ca.The potential of a series of anion‐ and cation‐exchange resin systems (AER and CER, respectively) as sinks for labile soil P was also examined. For all soils studied, P extracted by AER‐HCO3