Facilitating charge-carrier separation and transfer is fundamentally important to improve the photocatalytic performance of semiconductor materials. Herein, two-dimensional hexagonal WO3 nanoplates were synthesized by a two-step route: rapid evaporation and solid-phase sintering. The as-prepared WO3 exhibits an enhanced activity of photocatalytic water oxidation compared to bulk monoclinic WO3. The electron dynamics analysis reveals that a more efficient charge-carrier separation in the former can be obtained, the origin of which can be attributed to an increased number of surface defects in hexagonal WO3 nanoplates. This work not only presents a novel and simple method to produce two-dimensional hexagonal WO3 nanoplates, but also demonstrates that surface defects and two-dimensional geometric structures can promote the charge separation, which may be extended to the design of other efficient photocatalysts.