A novel CuO-CeO2-CoOx nanocatalyst was prepared for heterogeneous Fenton-like reaction to break the Ni2+-chelate into free Ni2+ in electroless nickel plating wastewater, followed by separation of Ni2+ in an insoluble form. The composite nanocatalysts prepared by co-precipitation method were characterized by XRD, TEM, and XPS, et al. Its catalytic activity as Fenton-like reagent was evaluated by the removal efficiency of Ni(II)-citrate after decomplexation and postprecipitation treatment. Subsequently, the effects of operating parameters on the decomplexation efficiency of the nanocatalysts were investigated including calcination temperature of catalysts, H2O2 concentration, catalyst dosage, initial pH and reaction temperature. Under optimized condition, the Ni(II)-citrate complexes (C-0 = 1.0 mM) achieved the complete decomplexation ( > 99.9%) within 60-mM reaction using 0.3 g/L of CuO-CeO2-CoOx calcined at 450 degrees C and 75 mM of H2O2 at pH 3.0 under 50 degrees C of reaction. Then, Ni2+ after decomplexation could be completely removed by the subsequent precipitation at pH 11.0. In addition, the life test of CuO-CeO2-CoOx catalyst indicated that, after recycled 10 times, its activity for decomplexation of Ni(II)-citrate decreased no more than 8%. As a result, this new heterogeneous Fenton-like process is promising for decomplexation and purification of electroless nickel plating wastewater as a sludge reduction technology.