Silicate sol-gel precursors of poly[bis(methoxyethoxyethoxy)phosphazene] and their corresponding hybrid networks were synthesized by hydrolysis and condensation reactions. Conversion of the precursor polymers to covalently interconnected hybrid networks with controlled morphologies and physical properties was achieved. Thermal analyses showed no melting transitions for the networks and low glass transition temperatures that ranged from approximately - 38 to - 67 degrees C. Solid solutions with lithium bis(trifluoromethanesulfonyl)amide in the network showed a maximum ionic conductivity value of 7.69 x 10(-5) S/cm, making these materials interesting candidates for dimensionally stable solid polymer electrolytes. (c) 2005 Elsevier B.V. All rights reserved.