TiO2 nanocones (TiO2-NCs) are constructed into arrayed spherical shells through a liquid-phase deposition reaction with polymer template, to improve the performance of TiO2 as anode of lithium ion microbattery. The morphology and structure characterizations indicate that TiO2 grows into nanocones with exposed {001} facets and is self-assembled into mesoporous structure. Meanwhile, macroporous channels are formed among the arrayed shells. Electrochemical measurements demonstrate that the TiO2-NCs reveal excellent performance in terms of improved lithium storage property and rate capability. The improved performance can be ascribed to the channel structure for the convenience of ionic transportation and the high-energy facets for the improvement of ionic reactivity.