High efficiency solar photocatalysis requires an effective separation of photogenerated charge carriers and their rapid transport to the semiconductor interface. The mechanisms and kinetics of charge separation and interfacial/interparticle charge transfers (CT) are significantly influenced by both the bulk and surface properties of the semiconductor. The surface properties are particularly important because the photocatalysis should be driven by the interfacial CT. The most popular and the most investigated semiconductor photocatalyst is based on bare and modified TiO₂. This article highlights the interfacial and interparticle CTs under the bandgap excitation of TiO₂ particles, visible light-induced photochemical processes via either dye-sensitization or ligand-to-metal CTs at surface modified TiO₂ particles, and the applications of the photo-processes to pollutant degradation and simultaneous hydrogen production. While a variety of surface modification techniques using various nanomaterials and chemical reagents have been developed and tested so far, their effects are very diverse depending on the characteristics of the applied photocatalytic systems and even contradictory in some cases. Better understanding of how the modification influences the photoinduced CT events in semiconductors is required, particularly for designing hybrid photocatalysts with controlled CTs, which is sought-after for practical applications of photocatalysis.