A study of vacuum-deposited organic–inorganic hybrid coatings for UV protection of polycarbonate is presented. UV-absorbing compounds which are commonly used for PC were embedded in a silica matrix by thermal co-evaporation. The hybrid layers were investigated by means of UV/VIS spectroscopy, FTIR spectroscopy and Laser induced fluorescence measurements. Next to the optical properties of the coatings, the stability of the intramolecular hydrogen bond (IMHB) and the influence of the silica network on the organic molecules are discussed. With UV irradiation experiments it could be shown that the hydroxyphenyltriazine compound shows higher UV stability in the hybrid coating than the hydroxybenzotriazoles.