Hollow ordered porous carbon spheres(HOPCS) with a hierarchical structure were prepared by templating with hollow ordered mesoporous silica spheres(HOMSS).Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) showed that HOPCS exhibited a spherical hollow morphology.High-resolution TEM,small angle X-ray diffraction(SAXRD) and N_2 sorption measurements confirmed that HOPCS inversely replicated the unconnected hexagonal-stacked pore structure of HOMSS,and possessed ordered porosity.HOPCS exhibited a higher storage capacity for Li~+ ion battery(LIB) of 527.6 mAh/g,and good cycling performance.A large capacity loss during the first discharge-charge cycle was found attributed to the high content of micropores.The cycling performance was derived from the hierarchical structure. Hollow ordered porous carbon spheres (HOPCS) with a hierarchical structure were prepared by templating with hollow ordered mesoporous silica spheres (HOMSS). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that HOPCS were a spherical hollow morphology. High- resolution TEM, small angle X-ray diffraction (SAXRD) and N 2 sorption measurements that the HOPCS inversely replicated the unconnected hexagonal-stacked pore structure of HOMSS, and possessed ordered porosity. HOPCS exhibited a higher storage capacity for Li ~ + ion battery (LIB ) of 527.6 mAh / g, and good cycling performance. A large capacity loss during the first discharge-charge cycle was found attributed to the high content of micropores. The cycling performance was derived from the hierarchical structure.