Porous Fe2O3 nanocubes composed of fine Fe2O3 nanoparticles have been facilely synthesized by simultaneous oxidative decomposition of Prussian blue (PB) nanocubes at high temperature. When evaluated as an anode material for lithium-ion batteries, the as-obtained porous Fe2O3 nanocubes manifest high specific capacity (∼800 mA h g−1 at 200 mA g−1) and excellent cycling performance.