This study was performed to better understand the chemical behaviour of P in a variety of alkaline soils from southern Australia. To do so, surface soil samples of 47 alkaline cropping soils from Upper Eyre Peninsula in South Australia and from western Victoria were collected. The 22 soils collected from Eyre Peninsula were Calcarosols, and those from western Victoria were Vertosols, Alkaline Duplex soils, Sodosols, and Red Brown Calcareous soils. Parameters included total and amorphous Al and Fe, organic C, organic P, CaCO3 content, P sorption characteristics, phosphorus buffer capacity, calcium lactate (Ca-Lac) extractable P, bicarbonate-extractable (Colwell) P, water-extractable P, anion exchange membrane extractable P (AEM-P), and isotopically exchangeable P (labile P). Concentrations of micronutrients in the Calcarosols were relatively low, considered to be a function of low clay contents. Given very low background Cd concentrations in the soils, it was estimated from Cd measurements that the majority of total P in the soils was derived from previous fertiliser applications. Phosphorus buffer capacities (PBCs) were relatively high in the Calcarosols and moderately high in the other alkaline soils. P sorption behaviour in the Calcarosols was a direct function of CaCO3 content, although in the other alkaline soils, amorphous Al and Fe oxides were the principal determinants of the P sorption behaviour. Both Colwell and Ca-Lac extractants dissolved non-labile P in the highly calcareous soils, whereas AEM appeared to only remove surface-adsorbed P. In addition, Colwell P values were positively related to PBC and to the slope term in the Freundlich model (Kf) when Kf > 10. It is suggested that AEM-P may be a better predictor of P availability in highly calcareous soils compared with the other extractants.