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Inverse photonic crystal films were prepared by photopolymerization of ethoxylate trimethylolpropane triacrylate (ETPTA) using opal-type templates. Their high quality was proved by investigations of structural and optical properties. The unexpectedly high refractive index, nETPTA ≈ 1.67, of polymerized ETPTA was obtained from a numerical approximation of the spectral positions of the reflectance peak of the films at different incidence angles. Fabricated samples were tested as sensors for water-ethanol mixtures, and a monotonous increase in the stop band shift with an increase in ethanol concentration was established.