Multi-shelled a-Fe2O3 hollow microspheres were synthesized using carbonaceous microsphere sacrificial templates and utilized for high capacity anode materials in lithium ion batteries (LIBs). Structural aspects including the shell thickness, number of internal multi-shells, and shell porosity were controlled by synthesis parameters to produce hollow microspheres with maximum lithium capacity and stable cycling behavior. Thin, porous, hollow microspheres with three concentric multi-shells showed the best cycling performance, demonstrating excellent stability and a reversible capacity of up to 1702 mA h g-1 at a current density of 50 mA g-1. The electrode performance is attributed to the large specific surface area and enhanced volumetric capacity of the multi-shelled hollow spheres that provide maximum lithium storage, while the porous thin shells facilitate rapid electrochemical kinetics and buffer mechanical stresses that accompany volume changes during de/lithiation.