We report a survey of the utilization of phosphazene materials in combination with metal alkoxide precursors to form ceramics through the sol–gel technique. Silicon, titanium, zirconium and aluminum three‐dimensional oxide networks were exploited for these investigations, while variably functionalized poly[bis(2,2,2‐trifluoroethoxy)phosphazene], poly[bis(methoxyethoxyethoxy)phosphazene] and poly[bis(4‐hydroxyphenoxy)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 ob‐served for the corresponding original polyphos‐phazenes. Copyright © 1999 John Wiley & Sons, Ltd.