Solid polymer electrolytes of high ionic conductivity are prepared using poly(vinyl alcohol) (PVA) complexed with various lithium salts such as LiClO4, LiCF3SO3 and LiBF4, and dimethyl phthalate (DMP) as plasticizer. The solid polymer electrolyte (SPE) films are characterized by X-ray diffraction, FTIR spectroscopy and ac impedance spectroscopic studies. Conductivity studies of these SPE films are carried out in the temperature range 302-373 K. The temperature dependence of the conductivity of polymer electrolyte films seems to obey VTF relation. (C) 2004 Elsevier B.V. All rights reserved.