CoO/Super P (conductive black) composites (CSP) were synthesized by a facile hydrothermal process followed by a heating treatment. The sample presents a porous CoO nanorod with inserted Super P structure. These CSP composites exhibit superior electrochemical performances in high Li-ion storage capacity (1020 mA h g−1 at 100 mA g−1) and rate capability (770 mA h g−1 at 1000 mA g−1) during the charge–discharge process. The specific role of Super P was further revealed to mainly accelerate the electrochemical reaction of CoO electrode during Li-ion insertion/extraction process. Thus, it shows much enhanced electrochemical performances compared with pure CoO.