Photocatalytic water splitting is the most promising process to convert solar energy into high purity chemical fuel (hydrogen), which has received significant attention in recent years. Only several photocatalysts have been reported in the literature for pure water splitting under visible light. Herein we report for the first time quantum sized BiVO4 can decompose pure water into H2 and O2 simultaneously under simulated solar light irradiation without any cocatalysts or sacrificial reagents. By electrochemical measurement, we demonstrate that the significantly different photocatalytic activity of the quantum sized BiVO4 arises from the negative shift of conduction band edge by a quantum confinement effect and a decreased overpotential for water reduction. Although the generated H2 and O2 are nonstoichiometric in the present study, these findings establish the great potential of using quantum sized BiVO4 photocatalyst and solar energy for overall water splitting.