A novel method has been developed to determine As-containing animal feed additives including roxarsone (ROX), p-arsanilic acid (p-ASA) and nitarsone (NIT), as well as other organic As species (dimethylarsonic acid (DMAA) and monomethylarsonic acid (MMAA)) by ion-pairing high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (IP-HPLC-HG-AFS). A simple isocratic reversed-phase (RP) HPLC method with a mobile phase containing citric acid and sodium hexanesulfonate (pH 2.0) was developed using a C(18) column. The use of an organic solvent free mobile phase turns this methodology into an environmentally friendly alternative. Several ion pair forming agents, such as sodium hexanesulfonate, tetrabutylammonium bisulfate and perfluoroheptanoic acid, were studied. The limits of detection for As species were calculated in standard solution and resulted to be 0.2, 0.5, 0.6, 1.6, and 1.6 μg As L(-1) for MMAA, DMAA, p-ASA, ROX and NIT, respectively. This method exhibited convenient operation, high sensitivity and good repeatability. It was applied to As speciation in different samples including arugula, dog food, dog urine and chicken liver.