A hierarchically Fe2O3@Co3O4 nanowire array is prepared by the aid of hydrothermal synthesis and sacrificial hydrolysis method. The obtained nanowire array shows hierarchical porosity and large surface area. The resulted Fe2O3@Co3O4 nanowire array is evaluated as an anode material for Li ion batteries, which exhibits high capacity and good cycle stability (1005.1 mAh g−1 after 50 cycles at a current density of 200 mA g−1) and an excellent rate performance, mainly owing to the unique hierarchical nanowire architecture and an elegant synergistic effect of two electrochemically active materials. The developed strategy can be readily generalized to construct other multifunctional hybrid nanostructures, which will be promising materials for high-performance electrochemical devices.