A novel flexible and lightweight Fe2O3-based lithium-ion battery anode has been developed by growing porous α-Fe2O3 nanorods onto carbon nanotubes–graphene foam (CNT–GF). The CNT–GF 3D network provides a highly conductive, high surface areas and lightweight scaffold for the active Fe2O3 nanorods. Such unique electrodes for lithium-ion battery exhibit an 80% initial columbic efficiency, high-rate capabilities, and >1000mAh/g capacities at 200mA/g up to 300 cycles without obvious fading. These properties can be attributed to the fast electrochemical reaction kinetics and electron transport rendered by the conductive 3D network. Our structural design protocol can be extended to many other nanostructured metal oxides or sulfides, and thus provides a new strategy for construction of high-performance electrodes for energy storage.