Ionic conductivity of poly(4-vinylpyridine) complexed with lithium salts has been investigated by complex impedance measurements and cyclic voltammetry. A polymer electrolyte prepared by complexing poly(4-vinylpyridine) with a nearly equal weight of lithium chloride in the presence of a nearly equal weight of pyridine showed a conductivity of 4.6 x 10(-3) S cm-1 at 20-degrees-C. A polymer electrolyte prepared by complexing poly(4-vinylpyridine) with a nearly equal weight of lithium perchlorate in the presence of a nearly equal weight of dimethyl formamide showed a conductivity of 4.3 x 10(-3) S cm-1 at 20-degrees-C. Ionic conductivities of these polymer electrolytes reached 10(-2) S cm-1 at 70-degrees-C.