Cr(VI) removal was investigated in a fixed-bed column using nanozerovalent iron-immobilized calcium alginate beads (nZVI-C-A beads) and a biofilm formed on nZVI-C-A beads. The removal studies were performed at various initial Cr(VI) concentrations, different flow rates, and bed heights. Under optimal conditions, nZVI-C-A beads showed 91.35 ± 1.57% Cr(VI) removal and 320.66 ± 3.87 mg/g removal capacity. For biofilm-coated nZVI-C-A beads, the removal percentage and removal capacity were found to be 97.84 ± 0.56% and 473.9 ± 4.84 mg/g, respectively. Breakthrough data were successfully described by the Thomas and Yoon-Nelson model for removal of Cr(VI) using nZVI-C-A and a biofilm on nZVI-C-A beads. Cr(VI) sorption on nZVI-C-A beads and biofilm-coated nZVI-C-A beads were confirmed by X-ray diffraction, energy-dispersive analysis of X-rays, and Fourier transform infrared. © 2016 American Chemical Society.