Based on direct reducing of copper ions by commercially available zero valent iron (ZVI), ZVI/Cu polyscale particles with high activation are synthesized and exhibit significant removal efficiency for reactive black (RB) dye. The ZVI/Cu polyscale particles could maintain a good performance for RB removal at a wide pH range of 3.0–9.0. Different from the mineralization process of other organic pollutants in ZVI/Cu system, the degradation kinetics of RB could be described well by novel pseudo‐second kinetic models. Results of scanning electron microscopy (SEM), X‐ray fluorescence elemental analysis (EDX), and X‐ray diffraction (XRD) show the planting Cu has deposited on the surface of Fe0. The characterization of ZVI/Cu particles and RB solution before and after degradation reveals that decolorization of RB is not only resulted from the reduction process including direct reduction by accepting electrons from Fe0 oxidation and indirect reduction by atomic hydrogen generated on the ZVI/Cu surface, but also the oxidation of hydroxyl radicals in the mineralization procedure of RB dye.