A series of cobalt oxide/multi-walled carbon nanotube (Co3O4/MWCNT) composites are successfully synthesized by a facile chemical co-precipitation method followed by a simple thermal treatment process. The morphology and structure of as-obtained composites are characterized by X-ray diffraction, scanning electron microscopy, and N2-adsorption/desorption measurements, and the electrochemical properties are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). For all Co3O4/MWCNT composites, MWCNTs are well dispersed in the loosely packed Co3O4 nanoparticles. Among them, the Co3O4-5%MWCNT composite exhibits the highest specific surface area of 137m2 g−1 and a mesoporous structure with a narrow distribution of pore size from 2 to 10nm. Because of the synergistic effects coming from Co3O4 nanoparticles and MWCNTs, the electrochemical performances of pure Co3O4 material are significantly improved after adding MWCNTs. The Co3O4-5%MWCNT composite shows the largest specific capacitance of 418Fg−1 at a current density of 0.625Ag−1 in 2M KOH electrolyte. Furthermore, this composite exhibits good cycling stability and lifetime. Therefore, based on the above investigation, such Co3O4/MWCNT composite could be a potential candidate for supercapacitors.