Abstract Photoinitiating systems combining 2,6‐diaminoanthraquinone (AQD), iodonium salt (Iod), and benzyl alcohol derivatives have been developed to efficiently initiate the cationic polymerization of epoxy monomers upon light exposure. Electron spin resonance spin‐trapping (ESR ST) experiments, fluorescence investigations, and steady‐state photolysis have demonstrated that a dye‐sensitized reaction occurs between AQD and the benzyl alcohol derivatives through a hydrogen abstraction mechanism upon light illumination, followed by reduction of Iod. The in situ liberation of protic acids promotes the cationic photopolymerization of epoxy monomers concomitantly with hydrolysis and condensation of the reactive methoxysilanes of an organic–inorganic precursor, for example, 3‐glycidyloxypropyltrimethoxysilane (GPTMS). Nanoindentation experiments and scratch resistance tests proved that the resulting GPTMS coatings exhibit very good resistance to brittle fracture and excellent adherence to stainless‐steel substrates. Interestingly, antibacterial tests of the GPTMS coatings showed efficient antifouling and biocide properties against E. coli and S. aureus .