Lithium and silver complexes, [Me(R)P=N]x[Me(R)P=N.M+BF4-]y (5a, M+ = Ag, R = Ph, x = 0.83, y = 0.17; 5b, M+ = Ag, R = Ph, x = 0.70, y = 0.30; 6, M+ = Ag, R = Me, x = 0.85, y = 0.15; 8, M+ = Li, R = Ph, x = 0.84, y = 0.16; 9, M+ = Li, R = Me, x = 0.80, y = 0.20), were prepared from [Me(Ph)PN]n (3) and [Me2PN]n (4) and AgBF4 or LiBF4. Each of these complexes had a single resonance in the P-31 NMR spectra suggesting mobility of the metal ions. However, two resonances were observed at -90-degrees-C in the spectrum of 9. A related polymer, [Me(Ph)PN]0.75[Me(Ph)PN.Ag(PPh3)+BF4-]0.25, 7, was also prepared. Treatment of 3 with PtCl2 resulted in both insoluble and soluble materials. Protonated forms of 3 and 4 were prepared by treatment with anhydrous HCl. Parent polymers were obtained from the proton complexes by washing with K2CO3 and from the silver complexes by treatment with NaCl. The new poly(phosphazene) complexes were characterized by H-1 and P-31 NMR spectroscopy, elemental analysis, and IR spectroscopy. Glass transition temperatures of these complexes range from -20-degrees-C for 9 to 121-degrees-C for 5b.