Beyond High‐Purity CO 2 : Material Innovations and Mechanistic Insights for Photocatalytic CO 2 Reduction under Close‐to‐Realistic Conditions

ABSTRACT Global climate change and the energy crisis pose severe challenges to sustainable development, driving the urgent need for innovative carbon‐neutral technological pathways. Among various potential solutions, photocatalytic CO 2 reduction technology attracts significant attention for its ability to directly utilize solar energy to convert CO 2 into high‐value‐added fuels and chemicals. However, in practical application environments, the low concentration of CO 2 and the pronounced inhibitory effect of oxygen on the catalytic reaction have long constrained the scalable development of this technology. This review systematically elaborates on the latest significant advancements in the field of photocatalytic CO 2 reduction under close‐to‐realistic conditions (containing 0.04% or 15% CO 2 and 5%–20% O 2 under simulated solar light), focusing on three main technological directions: integrated CO 2 capture and conversion, CO 2 ‐preferential microenvironment engineering, and O 2 ‐assisted CO 2 reduction mechanisms. These interconnected research pathways have collectively driven a paradigm shift in the field from “passively avoiding oxygen interference” to “actively harnessing oxygen synergy.” This progress has preliminarily overcome key bottlenecks such as low conversion efficiency of dilute CO 2 , intense competitive oxygen reduction reactions, and high energy consumption for product separation. These advancements provide the way for distributed carbon‐neutral technologies and shifting CO 2 utilization from idealized systems toward real‐world applications.