Several solvent mixtures and techniques for the extraction of arsenic (As) species from rice flour samples prior to their analysis by HPLC–ICP-MS were investigated. Microwave-assisted extraction using water at 80°C for 30min provided the highest extraction efficiency. Total recoveries of extracted As species were in good agreement with the total As concentrations determined by ICP-MS after microwave-assisted acid digestion of the samples. Arsenite [As(III)], arsenate [As(V)] and dimethylarsinic acid (DMAA) were the main species detected in rice flour samples.