Organic-inorganic UV-curing of organosilanes containing epoxy and trialkoxysilyl functional groups in the same monomer was implemented using a diaryl iodonium salt as cationic photoinitiator. UV-generated Bronsted acids through photolytic degradation Were found to be effective in catalyzing both epoxy ring-opening polymerization and alkoxysilane sol-gel polycondensation reactions. Competition between the formation of inorganic and organic phases was kinetically studied using real-time Fourier transform infrared spectroscopy (RT-FTIR). The nature of the hybrid monomer. the effect of changing the film thickness, the type of substrate and the influence of laminated conditions oil the polymerization kinetics were assessed. Si-29 and C-13 solid state NMR measurements were also performed to investigate the structure of the UV-cured hybrid materials.