Abstract: Allophane is a soil clay constituent with high adsorption capacity for cationic and anionic solutes and the adsorption characteristics depend on its Si/Al molar ratio. Adsorption experiments of phosphate and oxalate on two natural allophane samples with low (0.67; KyP) and high (0.99; KnP) Si/Al ratios were conducted at initial adsorbate concentration of up to 0.6 mM and at pH of 5.0 to 7.0. In both single and binary (equimolar phosphate and oxalate) adsorbates systems, KnP had less capacity for adsorption of both phosphate and oxalate than KyP had, because in the structure of KnP, accessory Si is already adsorbed onto aluminol groups to which phosphate and oxalate will be adsorbed. For KyP with lower Si/Al ratio and higher adsorption capacity, the efficiency of phosphate to depress the adsorption of coexisting oxalate, EOXâ†?P, was always greater than the reverse efficiency, EPâ†?OX, at a same condition; the ratio of oxalate/phosphate adsorbed in the binary system was less than unity and the ratio decreased with increasing pH and initial adsorbate concentration. These indicated higher selectivity of KyP for phosphate than for oxalate and the selectivity increased with increasing the competition between phosphate and oxalate toward KyP. KnP with higher Si/Al ratio showed higher selectivity for phosphate than KyP did, but the ratio of oxalate/phosphate adsorbed was almost constant when pH and initial adsorbate concentration were raised. This means that even under the lowest pH and the lowest adsorbate concentration examined (pH 5.0, 80 μM), the competition between phosphate and oxalate toward KnP was already severe and further increase in the phosphate selectivity was not caused.