In recent years, tetraethyl orthosilicate (TEOS) has been used as a precursor in preparing inorganic glasses. The technique, known as the sol‐gel process involves a two step poly(hydrolysis‐condensation)reaction sequence. The work presented here is concerned with the utilization of a suitably functionalized oligomeric “glassy” organic polymeric component in this two step sequence. In particular, an amine terminated amorphous poly(arylene ether) ketone, (PEK), end capped with isocyantonropyl triethoxy silane was used to synthesize a hybrid network with TEOS. Low incorporation of the PEK oligomers into the network caused by early vitrification can be eliminated by carrying out reactions at elevated temperatures. A systematic change in mechanical and physical properties of the hybrid glass has been found with TEOS content and the annealing temperatures. A model for the network has been proposed based on structural and morphological evidence.