Hybrid materials of poly(ethylene oxide-co-epichlorhydrin), HYDRIN, and silica were prepared by a sol-gel process. An inorganic network was grown in a tetrahydrofuran/organic polymer solution from acid hydrolysis and polycondensation of tetraethoxysilane, TEOS. During solvent evaporation and simultaneous growth of the inorganic network, phase separation was observed. The mechanism of phase separation of these sol-gel systems was investigated by light scattering. Spinodal decomposition (SD) was observed far HYDRIN/TEOS systems with composition equal to 71/29, 67/33, 60/40, 50/50, 40/60, 33/67 and 29/71. The morphology of the final HYDRIN/TEOS hybrid material was investigated by scanning electron microscopy. The thermal properties of these materials were investigated by differential scanning calorimetry and their hydrophilicity was evaluated by contact angle measurements.