We report a survey of the utilization of phosphazene materials in combination with metal alkoxide precursors to form ceramics through the solâgel technique. Silicon, titanium, zirconium and aluminum threeâdimensional oxide networks were exploited for these investigations, while variably functionalized poly[bisÂ(2,2,2âtrifluoroethoxy)phosphazene], poly[bisÂ(methoxyethoxyethoxy)phosphazene] and polyÂ[bis(4âhydroxyphenoxy)phosphazene] were used as phosphazene substrates. The resulting new hybrid materials, characterized by SEM, EDAX, DTA, TGA, DSC, DMTA and impedance techniques, showed improved thermal and mechanical stability, and higher ionic conductivity when doped with Li+ or Ag+ triflates, than those obâÂserved for the corresponding original polyphosâÂphazenes. Copyright © 1999 John Wiley & Sons, Ltd.