Ionic conductivity (10-4 S/cm at 25°C) has been observed in glassy poly(vinyl alcohol)/lithium salt complexes. X-ray diffraction patterns indicate that, while the pure polymer is semi-crystalline, the addition of salt suppresses the extent of crystallinity. The glass transition temperatures of these systems are typically in the region of 50-70°C. The conductivity is dependent on the concentration and anion in the lithium salt; LiClO4 producing the highest conductivities in this work. The presence of unhydrolyzed acetate groups in the polymer backbone causes Tg to be decreased, as compared to the homopolymer, and produces an order of magnitude increase in conductivity. 7Li solid state NMR spectroscopy suggests that lithium ion motion is present below Tg indicating that, at least in part, lithium ion motion is responsible for the ionic conductivity and that this motion is decoupled from the polymer segmental motions. 19F T1 and T2 NMR relaxation times were also measured for the anion, and the lack of correlation with the conductivity data suggests anion motion is unlikely to be a major contributor to the conductivity.