Iron oxide nanoparticles (IONPs) can play a significant role in the cycling of heavy metals. Arsenite [As(III)] is highly toxic, mobile, and predominant species in arsenic-contaminated groundwater. IONPs have been synthesized and tested for the removal of As(III) from arsenic contaminated water. In this work, we synthesized IONPs, as a finely divided loose nanopowder, using a chemical method involving a dispersion of the metal cations (Fe3+) through polymer molecules of polyvinyl alcohol (PVA) in an aqueous medium. X-ray diffraction (XRD) analysis confirmed the formation of a single phase rhombohedral crystal structure of R3c space group. Transmission electron microscopic images corroborate the result of IONPs of 45 nm average size and the rhombohedral shape. Selective experiments, conducted with an initial concentration of 0.25 ppm of As(III), have demonstrated the maximum As(III) adsorption capacity (96%) in 2.0 gL(- 1) IONPs in water at pH 4.5-7.5. At room temperature, the adsorption isotherm studies have revealed a better correlation with the Langmuir isotherm than the Freundlich isotherm. Characteristic surface hydrolysis of IONPs as = Fe-OH species has been studied in terms of the vibration bands. The results reveal that the removal of the As(III) species from water is associated with the As(III) adsorption onto the IONPs followed by a surface hydrolysis of the iron species.