Owing to their fundamental importance and practical applications, anatase TiO2 crystals with well-defined {001} and {101} facets attracted intensive research interests. In this study, we systematically investigated solvent dependence of the photoreaction of the different coexposed crystal facets during noble metal photodeposition. By examining the deposition position in each solvent, we revealed that solvents play a pivotal role on the facet selectivity. On the basis of density functional theory calculations, the solvent molecules were found to modify both the crystal facet electronic structure and the {001}-{001} heterojunction. These modifications are not only the origin of diverse charge-carrier pathways but are also responsible for carrier accumulation at specific facets that increase their reductive power. These findings are vital for a better understanding of photocatalytic materials and an improved design for the next-generation materials.