Thermal processing or the digestion process can alter the forms of arsenic (As) present in food. Identification of As species is necessary to accurately determine the risk associated with food consumption. X-ray absorption near-edge structure (XANES) was used to investigate As species in rice, asparagus, and garlic boiled in water containing As(V), and in their bioaccessible fractions (solubilized As after gastrointestinal digestion). The XANES analysis revealed the presence of As(III) (11871.5 eV) or As(III)-S [As(III)-Cys, 11869.6 eV] solution in the cooked foods and in their bioaccessible fractions. The percentage of trivalent species (12-55%) followed the order asparagus ≫ rice ≈ garlic. In the asparagus and garlic samples, part of the As(V) (tetrahedral form) [11875 eV] that had been added appeared in the form of an octahedral As(V) compound [As(V)-glycerol, 11876 eV]. All these changes could considerably modify the risk associated with ingestion of As-contaminated food.