Mesoporous single crystals (MSCs) rendering highly accessible surface area and long-range electron conductivity are extremely significant in many fields, including catalyst, solar fuel, and electrical energy storage technologies. Hematite semiconductor, whose performance has been crucially limited by its pristine poor charge separation efficiency in solar water splitting, should benefit from this strategy. Despite successful synthesis of many metal oxide MSCs, the fabrication of hematite MSCs remains to be a great challenge due to its quite slow hydrolysis rate in water. Herein, for the first time, we have developed a synthetic strategy to prepare hematite MSCs and systematically investigated their growth mechanism. The electrode fabricated with these crystals is able to achieve a photocurrent density of 0.61 mA/cm2 at 1.23 V vs RHE under AM 1.5G simulated sunlight, which is 20 times higher than that of electrodes made of solid single crystals. The enhancement is ascribed to the superior light absorption and enhanced charges separation. Our results demonstrate the advantage of incorporation of nanopores into the large-sized hematite single crystals and provide a valuable insight for the development of high performance photoelectrodes in PEC application.