The distinct features of UV induced polymerization of epoxy-acrylate blends leading to the formation of simultaneous interpenetrating polymer networks (IPNs) have been studied. Different ratios of components within a prevailing content of an epoxy one have been used for the synthesis. Such a content of epoxy monomer is required to create a barrier preventing oxygen diffusion into a curing sample. It allows retardation of the well-known oxygen-inhibition effect, which acrylate monomers are susceptible to. Hence, the conduction of their polymerization in open-air conditions is possible. The proceeding of the polymerization reactions of acrylate (TEGDM) via free radical mechanism and of epoxy (UP-650D) via cationic one have been monitored by FTIR-spectroscopy. Namely, the conversion degrees have been calculated for double bonds of TEGDM and for epoxy groups of UP-650D respectively. A mixture of triphenylsulfonium hexafluorophosphate salts, which is capable of generating both free radical and cationic reactive species, have been used as a single photoinitiator for the formulations being investigated. Almost complete conversion of acrylate double bonds was reached after 60 min of UV irradiation irrespective of epoxy content. On the contrary, conversion of epoxy groups of aliphatic epoxy, which is known to be rather unreactive towards cationic photopolymerization, when mixed may be either higher or lower compared to the neat epoxy network. Such results are attributed to dual influence of acrylate network on the formation of epoxy one. Firstly, cationic polymerization of epoxy component is sensitized by acrylate macroradicals in terms of free radical promoted cationic polymerization. On the other hand, the mobility of epoxy macrocations is restricted by the rapid build-up of acrylate network. At the weight ratio of UP-650D and TEGDM 70/30 the sensitizing effect of acrylate is revealed to be dominant, so the given composition may be considered as optimal. Regardless of low conversion of epoxy groups, the content of the estimated gel fraction is high, and the epoxy component is found not to be leached in the process of extraction in acetone. Furthermore, physicomechanical properties of obtained UV-cured IPNs have been investigated. The results of the measurements, namely, impact resistance by the Gardner test, crosshatch adhesion test to different substrates (including silicon), and accelerated weathering test in a climatic chamber, show that all the samples exhibit good operational properties essential for effective protecting coatings of outdoor exposure.