BiVO4 mesoporous single crystals (MSCs) were successfully prepared, for the first time, by a one-step hydrothermal method using the acidified BiVO4 precursor solution pre-impregnated silica as the template. It was revealed that the BiVO4 MSCs were formed by a double-diffusion mechanism. The O2 evolution rate over BiVO4 MSCs was improved nearly 10 times than that over BiVO4 bulk single crystals.