Abstract Hexavalent chromium existing in the effluent is a major concern for the metal-processing plant. In this study, a new method combining nanoparticle adsorption and magnetic separation was developed for the removal and recovery of Cr(VI) from wastewater. The nanoscale maghemite was synthesized, characterized, and evaluated as adsorbents of Cr(VI). Various factors influencing the adsorption of Cr(VI), e.g., pH, temperature, initial concentration, and coexisting common ions were studied. Adsorption reached equilibrium within 15 min and was independent of initial Cr concentration. The maximum adsorption occurred at pH 2.5. The adsorption data were analyzed and fitted well by Freundlich isotherm. Cr(VI) adsorption capacity of maghemite nanoparticles was compared favorably with other adsorbents like activated carbon and clay. Competition from common coexisting ions such as Na +, Ca 2+, Mg 2+, Cu 2+, Ni 2+, NO 3 −, and Cl − was ignorable, which illustrated the selective adsorption of Cr(VI) from wastewater. Regeneration studies verified that the maghemite nanoparticles, which underwent six successive adsorption–desorption processes, still retained the original metal removal capacity. In addition, the adsorption mechanisms were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopic techniques.