The effects of radiata pine (Pinus radiata D. Don) seedlings and ryegrass (Lolium perenne L.) on the mineralisation of orthophosphate monoesters in 7 grassland soils were assessed in a 10-month pot trial using NaOH-EDTA extraction and solution 31P NMR spectroscopy. Extraction with NaOH-EDTA recovered 46-86% of the total soil P, and NaOH-EDTA-extractable organic P determined by molybdate colourimetry ranged between 194 and 715 mg/kg soil, representing 34-85% of the total soil organic P. Orthophosphate monoesters were the predominant species of the extracted organic P in all soils, with much smaller concentrations of orthophosphate diesters, and traces of phosphonates. Concentrations of orthophosphate monoesters were consistently lower in soils under pine (103-480 mg P/kg soil) compared with the initial soils (142-598 mg P/kg soil) and most soils under grass (122-679 mg/kg soil). Mineralisation of myo-inositol hexakisphosphate accounted for 18-100% of the total mineralisation of orthophosphate monoesters in most soils under radiata pine. This suggests that supposedly recalcitrant inositol phosphates are available for uptake by radiata pine, although the extent of this varies among soils.