Raman spectroscopic studies were carried out for hybrid polymer thin films prepared for photonic applications by the sol-gel technology. Our aims were to analyse the ability of the Raman method toestimate the efficiency of the main reactions of the sol-gel process and to provide information about the chemical composition of the films as well as their thickness, profile, and quality. The difficulties in measurement such as low level of Raman signals, difficulties in data analysis caused by the complex structure of the materials, and the influence of interfering signals, are discussed. The application of Raman microscopy for characterising films based on 3-glycidoxypropyl-trimethoxysilane (GPTS), methacryloxypropyltrimethoxysilane (MPTS), and 3-aminopropyl-trimethoxysilane (APTES) is presented. The efficiencies of reactions of inorganic and organic polymerisation were measured and their products have been identified. The influence of the excitation beam wavelength as well as the type of substrate on the Raman spectra was investigated. Moreover, two-dimensional Raman mapping enabled us to record the thickness profiles of the deposited structures and to detect their defects.