A series of quaternized poly(2-vinylpyridine) (PVP) polymers has been synthesized with the general formula [(PVP)R]I, where R=H, Me, Bu. Addition of AgI to the polymers results in new silver ion conducting solid polymer materials. Conductivities as high as 6x10(-3) S/cm have been observed for the 3:1 AgI/[(PVP)Me]I composition. Analogous materials with a 3:1 composition for the protonated and butyl-substituted polymers display lower conductivities near 2 x 10(-4) S/cm. Conductivity studies, as a function of temperature, show these materials to be thermodynamically stable with a low activation energy for ion conduction. Differential scanning calorimetry experiments suggest that a new phase with the general formula (PVP)RAg3I4 forms with silver ions in a new amorphous state. (C) 2003 Elsevier B.V. All rights reserved.