Novel polyelectrolytes were synthesized by quaternization of the backbone of poly(alkoxy- and aryloxyphosphazenes) with strong alkylation reagents. As models for the synthesis of these polymers, similar quaternization reactions were also carried out on small-molecule alkoxy and aryloxy cyclotriphosphazenes. The quaternized small molecules and high polymers were characterized by H-1 NMR, P-31 NMR, DSC, TGA, and AC impedance studies. The quaternized poly(alkoxyphosphazenes) showed ionic conductivities of 2.58 x 10(-4) S.cm(-1) at 25 degrees C and 2.09 x 10(-3) S.cm(-1) at 80 degrees C, which are among the highest values for known solvent-free ionically conducting polymers.