Understanding the relation between a crystal facet and photocatalytic performance is of great importance for the development of effective catalysts. In this work, we focus on anatase TiO 2 with controllable exposed facets toward photocatalytic hydrogen evolution by water splitting. By combining temperature-programmed desorption (TPD) and diffuse reflectance infrared spectroscopy (DRIFTS), we obtain that the adsorption of hydroxyl groups and the photo-driven breaking of hydroxyl groups depend strongly on the exposed facets. As a result, the higher catalytic hydrogen evolution activity of TiO 2 enclosed with (101) facets than that of (001) facets should be ascribed to the more favorable depletion of hydroxyl groups. Moreover, graphene quantum dots (GQDs) with rich surface functional groups are deliberately deposited on the TiO 2 surface. The determination of the states and dynamics of surface hydroxyl groups suggests that GQDs facilitate the reaction of hydroxyl groups on (001)TiO 2 , thus leading to the activity enhancement. By contrast, the already active (101)TiO 2 become apparently less efficient after GQD deposition due to the restricted reaction of hydroxyl groups. Overall, our findings not only provide a unique guidance for understanding the crystal-plane-dependent photocatalysis but also present a powerful approach by which to tailor the photocatalytic performance.