Solar photocatalysis is emerging as an environment‐friendly and sustainable energy approach for the production of fine chemicals and pharmaceuticals with high industrial and academic importance. Due to photochemical stability, tunable redox capability, and facile recyclability, semiconductor photocatalysts display remarkable advantages over molecular photocatalysts, thus attracting increasing attention. More importantly, photoexcited hole–electron pairs on semiconductor photocatalysts can accomplish two aligned redox reactions on the same semiconductor surface, resulting in unique designs of several semiconductor photocatalysis models. This review surveys recent advances in rational harnessing of photoexcited hole–electron pairs in semiconductor photocatalysts for oxidative and reductive synthetic transformations for chemical and pharmaceutical production. Depending on the catalytic behavior of the photogenerated redox centers, there are three major semiconductor photoredox reaction modes: 1) photoexcited hole‐induced oxidations, 2) photoexcited electron‐induced reductions, and 3) photoexcited electron–hole pairs co‐induced redox‐neutral reactions. The characteristics, reaction scopes, and mechanisms of these three semiconductor photocatalysis modes are discussed. Finally, the major challenges and future opportunities regarding the rational design of photoexcited redox centers in advanced synthetic chemistry are provided.