One dimensional porous NiO-decorated Co3O4 composites were synthesized via a two-step solution-based method. The composites were detected by X-ray photoelectron spectroscopy (XPS), and it shows that the atomic ratio of nickle is about 1.74% in the composite. The obtained NiO-decorated Co3O4 composite yields a high specific capacitance of 1112Fg−1 at a current density of 2Ag−1, exhibits perfect rate and cycling stability. Furthermore, the specific capacitance of the composite can still keep a good retention of 97% after 1000 cycles at 2Ag−1, demonstrating the excellent long-term electrochemical stability of the composite.