Ion foam fractionation is a green and cost-effective technology where separation of molecules exploits the difference in surface affinity. In this work, a batch ion foam fractionation system was designed and optimized for the separation of trace hexavalent chromium (Cr(VI)) from aqueous solutions. The effect of surfactant head groups (collectors) on the adsorption dynamics was analyzed. Cetyl trimethyl ammonium bromide (CTAB), a cationic surfactant showed high efficiency for the removal of Cr(VI) from aqueous solutions. An experimental investigation of the effect of different operational parameters on the separation characteristics is presented. The recovery of Cr(VI) increased with the increase in CTAB/Cr(VI) molar ratio and reached a maximum of 92.5% at optimum operating conditions. However, with CTAB concentrations close to the critical micelle concentration (CMC) wet foams were produced resulting in high liquid hold-up and poor enrichment ratio. The presence of Cr(VI) at the gas-liquid interface significantly improved the drainage characteristics of the foam decreasing the liquid hold-up. Further, a three-stage ion foam fractionation unit was developed with Cr(VI) removal efficiency of more than 99%. The concentration of Cr(VI) in the residue after the three-stage operation was less than 0.02 mg/L which is below the USEPA recommended standards for drinking water. © 2018 Elsevier B.V.