Two series of new phosphazene polymer electrolytes, PPAP/LiClO4 and PHAP/LiClO4, were prepared by complexing lithium perchlorate, LiClO4, to poly(bis(pentylamino)phosphazene), PPAP, and poly(bis(hexylamino)phosphazene), PHAP, respectively. The electrolytes were characterized by the combination of FTIR, P-31-NMR, and C-13-NMR spectroscopies. Films of these electrolytes showed good dimensional stability and ionic conductivity. The glass transition temperatures were determined by differential scanning calorimetry. The highest ionic conductivity, sigma, was 7 orders higher in magnitude than the sigma of its parent polymer and was similar to the sigma of PEO at room temperature. The plots of ionic conductivity versus temperature for the polymer electrolytes were found to correspond to the Vogel-Tammann-Fulcher equation throughout the temperature range 30-100 degrees C.