Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.