Catalyst‐Free Aerobic Photooxidation: Mechanistic Pathways and Sustainability Perspectives

Catalyst‐free aerobic photooxidation represents an increasingly important strategy for visible‐light‐driven oxidative synthesis using molecular oxygen as the terminal oxidant. In these transformations, substrate excitation or electron donor–acceptor (EDA) interactions directly activate O 2 through energy transfer, single‐electron transfer, hydrogen‐atom transfer, or EDA‐mediated pathways, enabling diverse oxidative reactivity without external photocatalysts or stoichiometric oxidants. Despite rapid growth of this field, these reactions have largely been discussed as isolated transformations rather than as a unified oxidative platform governed by common photoactivation principles. This review provides a unified mechanistic and operational framework for catalyst‐free aerobic photooxidation. Reported systems are organized into six major reaction classes, establishing recurring relationships between activation modes, oxygen‐derived intermediates, and oxidative reactivity. The review further discusses sustainability and operational implications arising from solvent choice and reaction conditions. Together, these perspectives establish catalyst‐free aerobic photooxidation as a conceptually unified platform for future sustainable oxidative synthesis.