A Raman spectroscopy was used to diagnose a synthesis process of new class of materials - hybrid polymer thin films, dedicated to planar optical waveguides. Hybrids, made in sol-gel technology, have a great application potential, because their properties may be formed in wide range. However, to obtain high quality product, a strict control of the manufacturing process must be ensured. In our experiment, correctness of particular steps of the process as well as molecular structure of monomers, gel and thin films was investigated. The results of Raman mesurements showed that efficiency of two basic reactions should be improved. However, the structure of final product seems to be appropriate. To investigate full potential of Raman spectroscopy in process control, an experimental in-situ measurement was made in the real time, which allowed us to estimate the time required for the reaction.