This paper reviews the photoinduced reactions of benzodioxinones and how they function in polymer synthesis and UV curing applications. The mechanistic characteristics of the ketene and benzophenone production from the photolysis of benzodioxinone indicate that, under certain conditions, each intermediate may undergo further reactions expedient for the formation of various polymeric structures. While ketenes are efficient contributors to step growth polymerization when subjected to reaction with the compounds possessing hydroxyl or amine groups, the released benzophenone can be utilized as a photoinitiator in both the free radical and cationic polymerizations. It has been shown that the photolysis of heterobifunctional monomers equipped with benzodioxinone and aliphatic hydroxyl groups leads to the formation of oligoesters with a narrow molecular weight distribution. We also validated the photochemical ability of benzodioxinone to induce the synthesis of block and graft copolymers, hybrid and branched polymers, and cross-linked monofunctional vinyl monomers or hydroxyl group-containing linear polymers.