Volcanic ash derived soils represent between 50-60% of the total arable land area of southern of Chile, and they are the most important soils for pasture production. In these soils, high phosphorus (P) fixation and, in turn, low P availability and high aluminium (Al) soluble concentrations (at low pH) are the most limiting factors for pasture production. At the same time, the complexes between Al-or iron-(Fe) and organic matter as well as short-range order alumino-silicates (allophane) allow the retention of huge quantities of soil P. The aim of this work was to assess the status of P by both sequential extraction procedure (Hedley) and 31 P-NMR analysis as influenced by Al and Fe in volcanic grasslands Andisols (Pemehue, Gorbea, Piedras Negras and Llastuco Soil Series) from Southern Chile. We applied Hedley chemical sequential fractionation to soils in order to examine the potential differences in extractable soil inorganic P (P i ) and organic P (P o ) fractions. We also determined total P and Olsen P in these grassland Andisols. Oxalate and pyrophosphate were employed to determine the active and organic matter complexed Al and Fe, respectively. Furthermore, we quantified Al and Fe in extracts of the Hedley P fractions. We found that Al extracted in oxalate was correlated positively with labile P o concentration, specifically with both the NaHCO 3 -P o (r=0.45, P≤0.01), and the NaOH-P o (r=0.43, P≤0.01) fractions. This observation was reinforced by 31 P-NMR analysis that showed higher monoester P and myo-IP 6 content in soils with higher amounts of oxalate Al. Hedley sequential fractionation procedure confirmed the role of Al in the NaOH-P o fraction for promoting P o storage, as both fractions were correlated (r=0.33, P≤0.05). In addition, Fe plays a substantial role in recalcitrant P accumulation as we found a high correlation between residual P and oxalate Fe (r=0.55, P≤0.01).