Manganese oxides have been done due to their relatively low conversion potential, small voltage hysteresis, high abundance and large theoretical capacity. However, manganese oxide has poor electronic conductivity and large volume variation during the discharge and charge processes. In this study, we tried to develop hollow nanostructure, which was made by self-assembly of manganese oxide and graphene oxide to improve their electrochemical properties. According the electron microscopy (SEM, TEM) images, the nanohybrids were found to have a spherical hollow structure. In the energy dispersive spectroscopy mapping, it was observed that the carbon and manganese oxide were homogeneously distributed in nanohybrids. In the electrochemical impedance spectroscopy, the nanohybrids had much higher electron conductivity than that of the pristine bulk manganese oxide. In the electrochemical application, lithium storage capacity of hollow nanostructure Mn3O4/RGO was significantly improved, compared with that of RGO. The obtained nanohybrids could be used as anode materials in Lithium ion batteries.