Novel porous ZnO/ZnFe2O4/C octahedra with hollow interiors are fabricated by a facile self-sacrificing template method involving the refluxing synthesis of hollow, metal-organic framework octahedra in solution and subsequent thermal annealing in N2 . When evaluated as an anode material for lithium-ion batteries, these porous hollow ZnO/ZnFe2O4/C octahedra exhibit significantly enhanced electrochemical performances with high rate capability, high capacity, and excellent cycling stability.