Size-controlled and high-index faceted α-Fe 2 O 3 nanocrystals with pseudocubic and rhombohedral morphologies were synthesized through the hydrothermal treatment of β-FeOOH at different pHs. The size effect on the photocatalytic oxygen evolution efficiency of high-index faceted α-Fe 2 O 3 nanocrystals was investigated. Rhombohedral α-Fe 2 O 3 (pH 6.0) exhibits an outstanding apparent quantum yield of 9.93% and an oxygen evolution efficiency of 20.3%, which can be attributed to the optimal size and high-indexed {104} planes. This work provides a new idea for the design of high activity water oxidation catalysts, through the size optimization of high-index faceted materials.