A column study was conducted using a combination of zero-valent iron (Fe 0) and iron oxide-coated sand (IOCS) for removing Cr(VI) and As(V) from groundwater. The removal efficiency and mechanism of Cr(VI) and As(V), the effects of humic acid (HA), and the various configurations of Fe 0 and IOCS were investigated. The results showed that the use of an Fe 0 and IOCS mixture in a completely mixed configuration can achieve the highest removal of both Cr(VI) and As(V), whilst the effects of HA were marginal in using these reactive materials. The solid phase analysis revealed the occurrence of the synergistic effect in these reactive materials as Fe 2+ can be adsorbed onto the IOCS and transform the iron oxides to magnetite, providing more reactive surface area for Cr(VI) reduction and reducing the passivation on the Fe 0. As(V) can then be removed by adsorption onto these iron corrosion products. HA can be adsorbed onto the IOCS so that the impacts of the deposition of HA aggregates on the Fe 0 surface can be reduced, thus enhancing the Fe 0 corrosion.