Chromium (Cr) contamination poses serious threats to the environment and human health. Thus, batch and column experiments were performed to investigate hexavalent chromium [Cr (VI)] removal from solution and porous media using nanoscale zerovalent iron nanoparticles (NZVI) stabilized by sodium carboxymethyl cellulose (CMC). Batch experiments indicated that the mass ratio of Fe/CMC = 1, the presence of 150–200 mg L−1 CMC and lower ionic strength led to optimum Cr (VI) removal in aqueous solution. Column experiments demonstrated that Cr (VI) removal was enhanced with decreasing solution pH and increasing CMC-NZVI concentration. The presence of CMC can increase Cr (VI) removal by NZVI in both aqueous solution and porous media by complexation precipitation of Cr (VI) compounds and better dispersion of NZVI. X-ray photoelectron spectroscopy (XPS) analysis revealed that an appropriate amount of CMC supported the redox reaction of Cr (VI) and NZVI. The removal of Cr (VI) through columns was 20.8% and 88.5% under no additional CMC and optimized CMC content, respectively. However, Cr (VI) removal decreased to 64.6% under excessive CMC content. The CMC modified NZVI nanoparticles were characterized by XRD, XPS and TEM techniques. These findings imply that CMC can be used as an effective stabilizer on NZVI which can in turn be applied for the efficient removal of Cr (VI) from industrial wastewater and groundwater.