Recent Advances in Transition‐Metal‐ and External Photocatalyst‐Free Photochemical Reactions

In recent years, transition‐metal‐ and external photocatalyst‐free photochemical reactions have garnered significant attention as environmentally friendly and sustainable approaches to organic synthesis. These reactions rely on either direct photoexcitation of substrates or photoexcitation of electron donor–acceptor complexes to enable diverse transformations. This review summarizes representative advances reported in the recent years, organized by the construction of C–C and C–heteroatom bonds, and highlights key mechanistic features. This review aims to provide guidance and inspiration for reaction design and mechanistic exploration in this field.