A novel treatment for chromium, vanadium and ammonium from vanadium industrial wastewater using a byproduct of magnesium-based wet flue gas desulfurization is investigated. In the present study, the byproduct is used as a reductant for chromium and vanadium removal by chemical precipitation, and the residual magnesium ion can also be used to remove ammonium in the present of phosphate by struvite crystallization. Besides, the effects of main operational parameters (reaction pH, byproduct dosage and reaction time) on the heavy metal removal and ammonium removal (reaction pH, Mg2+:NH4+:PO43-molar ratio and reaction time) are investigated, and the reaction mechanism for this treatment technology is also proposed. Under the optimal conditions, the residual concentrations of chromium(IV), total chromium and vanadium are 0.046 mg/L, 0.468 mg/L and 0.06 mg/L, respectively. The removal efficiency of ammonium is 95.72% and the residual concentrations of ammonium and phosphorus are 137.12 mg/L and 5.49 mg/L, respectively. Additionally, the precipitations are characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and thermogravimetry differential scanning calorimetry (TG-DSC), respectively. Finally, a resource utilization method of the precipitation sludge from this technology is also presented. (C) 2017 Elsevier B.V. All rights reserved.