 The synthesis of ultra-small cobalt-doped (Co-doped) Mn3O4 nanoparticles tiled on multilayer graphene (MLG) surface by one-pot hydrothermal method was reported here. MLG was obtained by the ultrasonication of expanded graphite in mixture solution of N,N-Dimethylformamide (DMF) and H2O and used without any further treatment. Co-doped Mn3O4 nanoparticles were in situ assembled onto MLG surfaces by van der Waals force between metal complex and MLG. The characterization by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that the as-prepared Co-doped Mn3O4 nanoparticles were homogeneously tiled on MLG with good crystallization and uniform size. The effects of cobalt doping content on the microstructure and electrochemical performance for the composites were studied. For Co0.45Mn2.55O4/MLG composite, a reversible capacity of 906 mAh g−1 is stably delivered at 100 mA g−1 based on the overall weight and it is maintained to 442 mAh g−1 at a high current density of 2 A g−1.