Urchin-like α-Fe2O3/MnO2 hierarchical hollow composite microspheres have been synthesized by using carbon as sacrificial templates. By combining the advantages of Fe2O3 with high electrical conductivity and MnO2 with high theoretical capacity, the urchin-like α-Fe2O3/MnO2 composites present better electrochemical performances as a lithium ion battery anode compared with α-Fe2O3 hollow spheres and MnO2 hollow spheres. The α-Fe2O3/MnO2 composites exhibit high initial discharge capacity of 1531 mAhg−1 and excellent reversible capacity of 860 mAhg−1 after 150 cycles at 0.1Ag−1. Furthermore, the composites retain a discharge capacity of 494 mAhg−1 after 500 cycles at 0.5 Ag−1. The excellent performances may originate from reinforced structural stability, large surface area and good electrical conductivity. The urchin-like α-Fe2O3/MnO2 composite material may serve as a potential anode material for lithium-ion battery.