Traces of P(V) and As(V) in sample solutions were converted into heteropoly molybdic acids at pH 1.5 and collected onto polyoxyethylene(20)-4-isononylphenoxy ether-coated Amberlite XAD-4 particles. The desorption was carried out with 0.3 M tetramethylammonium hydroxide solution for the HPLC analysis. Molybdophosphoric and molybdoarsenic acids were separated from excess molybdate by ion-pair reversed phase HPLC, though the peaks of P(V) and As(V) could not be resolved. However, the selective decomposition of molybdoarsenic acid with citric acid allowed the differential determination of P(V) and As(V) at the ng mL -1 level. The proposed method was applied to the analysis of high-purity iron for P and As.