The utilization of CO2, H2O, and solar energy is regarded as a sustainable route for converting CO2 into chemical feedstocks, paving the way for carbon neutrality and reclamation. However, the simultaneous photocatalytic CO2 reduction and H2O oxidation under non‐sacrificial ambient conditions is still a significant challenge. Researchers have carried out extensive exploration and achieved dramatic developments in this area. In this review, we first primarily elucidate the principles of two half‐reactions in the photocatalytic conversion of CO2 with H2O, i.e., CO2 reduction by the photo‐generated electrons and protons, and H2O oxidation by the photo‐generated holes without sacrificial agents. Subsequently, the strategies to promote two half‐reactions are summarized, including the vacancy/facet/morphology design, adjacent redox site construction, and Z‐scheme heterojunction development. Finally, we present the advanced in situ characterizations and future perspectives in this field. This review aims to provide fresh insights into effectively simultaneous photocatalytic CO2 reduction and H2O oxidation under non‐sacrificial ambient conditions.