Nanodimensional monodispersed Cu–MnO heterostructures were synthesized via a facile solution-based method. Cu–MnO heterostructures with narrow size distribution were successfully achieved in the presence of organic surfactants to prevent agglomeration during the growth process. Furthermore, the unique architecture of carbon-coated Cu–MnO (Cu–MnO@C) core–shell heterostructures obtained after a thermal annealing process preserved the electrical integrity of the electrode via the conductive copper “nanobridge” to provide an efficient electron transfer pathway between the active materials and the current collector. On the other hand, the amorphous carbonaceous shell evidently gives a protective layer to attain structural integrity throughout the electrochemical measurements. Enhancement in the electrochemical performance can be reflected by the excellent cycling stability and high rate capability of the Cu–MnO@C heterostructures as compared to the MnO@C nanoparticles.