A series of CoO/reduced graphene oxide (CoO/RGO) composites with different proportions are successfully synthesized via a hydrothermal method. As an additive for the nickel-based alkaline secondary battery cathode, the electrochemical performances of the proposed CoO/RGO composite are systematically investigated on its cyclic stability, rate capability, capacity recovery performance, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), in comparison with commercial CoO. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) images show that the CoO nanoparticles are in-situ anchored on the surface of soft and flexible graphene sheets. Electrochemical results indicate that the CoO/RGO composites exhibite the highest performance when the weight ratio of CoO and RGO is 5:5. The optimized CoO/RGO composites as an additive for the nickel electrode not only can substantially reduce the CoO additive but also possess good electrochemical performances, especially for the high-rate capability. The discharge capacity of the nickel electrode with 5wt% of CoO/RGO (5:5) addition deliver a high discharge capacity of 284.3, 264.6,235.4 and 208.6mAhg−1 at 0.2, 1.0, 5.0 and 10.0C, respectively. The capacity recovery rate at 0.2C can reach 98.4%. CV and EIS test indicate that the incorporation of RGO can significantly enhance the reversible property, current density of cathodic peak, proton diffusion and conductivity of the nickel electrode.