The charge migration mechanism across the surface heterojunction constructed on an anatase TiO2 nanocrystal is still under debate. To solve this longstanding question, we present a systematic study of the band edges (vs. standard hydrogen electrode, SHE) of aqueous TiO2 interfaces with anatase (101), (100) and (001) surfaces, using a combination of density functional theory-based molecular dynamics (DFTMD) and efficient computational SHE (cSHE) methods. Our calculations show that the conduction band minimum (CBM) of the (101) surface is lower than that of (001) and (100) surfaces, which is thermodynamically favorable for electrons migrating to the (101) surface through the surface heterojunction, while the hole preferentially accumulates on the (100) surface due to its highest valence band minimum (VBM). In addition, we qualitatively explore the facet-dependent photocatalytic activity of anatase TiO2. Due to the possession of both the beneficial atomic structure (with 100% undercoordinated Ti5c atoms at the surface) and electronic structure (more strongly oxidizing holes in the VBM and efficient electron-hole spatial separation separation), the (001) surface exhibits the most efficient photocatalytic performance for water oxidation. Furthermore, it is confirmed that the use of simplified theoretical models neglecting the detailed atomic structures of water at the aqueous interface is inadequate to predict the band alignment of semiconductors relative to water redox potentials, so that it may result in substantial errors in evaluating the photocatalytic performance of materials to be used for water splitting.