A structurally hierarchical MnO2/TiO2 composite (Nano-MnO2@TiO2) is fabricated by calcining MnCO3 microspheres and coating a thin layer of TiO2 through the heat decomposition of tetrabutyl titanate, and evaluated as anode of gravimetrically and volumetrically high energy density lithium ion battery. The characterizations from FESEM, TEM, HRTEM and XRD, indicate that the resulting Nano-MnO2@TiO2 takes a spherical morphology with a core of about 2 μm in diameter, consisting of compact MnO2 nanoparticles, and a shell of 60 nm thick, consisting of smaller TiO2 nanoparticles. The charge/discharge tests demonstrate that Nano-MnO2@TiO2 exhibits excellent performance as anode of lithium ion battery, delivering a capacity of 938 mAh g−1 at 300 mA g−1 after 200 cycles, compared to the 103 mAh g−1 of the uncoated sample. The microsphere consisting of compact nanoparticles provides Nano-MnO2@TiO2 with high specific gravity. The dimensionally and structurally stable TiO2 maintains the integrity of MnO2 microspheres and facilitates lithium insertion/extraction. This unique structure yields the excellent cyclic stability and rate capability of Nano-MnO2@TiO2.