Fe2O3 microboxes with hierarchically structured shells have been synthesized simply by annealing Prussian blue (PB) microcubes. By utilizing simultaneous oxidative decomposition of PB microcubes and crystal growth of iron oxide shells, we have demonstrated a scalable synthesis of anisotropic hollow structures with various shell architectures. When evaluated as an anode material for lithium ion batteries, the Fe2O3 microboxes with a well-defined hollow structure and hierarchical shell manifested high specific capacity (950 mA h g–1 at 200 mA g–1) and excellent cycling performance.