The polymer electrolytes comprising blend of poly(vinyl acetate) (PVAc) and poly(methylmethacrylate) (PMMA) as a host polymer and LiClO4 as a dopant are prepared by solution casting technique. The amorphous nature of the polymer-salt complex has been confirmed by XRD analysis. The DSC then-nograms show two T-g's for PVAc-PMMA blend. A decrease in T-g with the LiClO4 content reveals the increase of segmental motion. Conductance spectra results are found to obey the Jonscher's power law and the maximum dc conductivity value is found to be 1.76 x 10(-3)S cm(-1) at 303K for the blend polymer complex with 20wt.% LiClO4, which is suitable for the Li rechargeable batteries. The conductivity-temperature plots are found to follow an Arrhenius nature. The dc conductivity is found to increase with increase of salt concentration in the blend polymer complexes. (c) 2006 Elsevier B.V. All rights reserved.