In this article the application of the sol-gel technique to phosphazene substrates to obtain a novel series of hybrid materials is revieved. Different types of phosphazenes are suitable for this goal, i.e. hexachlorocyclophosphazene and polydichlorophosphazene, alkoxy-substituted phosphazene substrates, phosphazene polymers bearing oligoethyleneoxyde or trifluoroethoxide moieties, phosphazene derivatives containg alkoxy or aryloxy groups functionalized with free hydroxyl functions, and cyclophosphazenes containing trialcoxysilane functionalities. For some of these materials only weak forces are involved between phosphzenes and the inorganic network ehen hybrid materialss are prepared. For others genuine chemical bonds are formed among them. In both cases relevant improvments for the applicability properties of phosphazene substrates are observed together with the onset of new features