Cr2O3-based nanospheres have been synthesized by a facile soft-template assisted method without sacrificing the template. Two types of Cr2O3 materials, the Cr2O3–C composite nanospheres (referred to as Cr2O3–C) with a novel hierarchical core/shell structure, and pure mesoporous Cr2O3 spheres (referred to as mesoporous Cr2O3) have been obtained by using a certain thermal treatment without adding more carbon precursor. The carbon coating layers in the Cr2O3–C composite distribute from the inside to the surface of the spheres continuously. Both the Cr2O3–C composite and the pure mesoporous Cr2O3 spheres are investigated with XRD, SEM, TEM, and electrochemical tests toward lithiumstorage. It is found that the reversible capacity for Cr2O3–C composite still retain more than 600 mA h g−1 even after 35 cycles, showing a capacity retention of 87%, while mesoporous Cr2O3 spheres and commercial Cr2O3 can only deliver a capacity of 320 mA h g−1 and 280 mA h g−1, respectively. The improvements can be attributed to the superiorities both in structure and in composition.