The solid polymer electrolyte consisting of a copolymer with epichlorohydrin and ethyleneoxide as host polymers and LiClO4 as the ionic dopant has been synthesized by solution casting technique. The amorphous nature of the polymer salt complex has been confirmed by XRD. From the DSC analysis it is found that the glass transition temperature (T-g) increases with the increase in LiClO4 concentration and this may be due to the formation of 'transient crossing knots'. The dielectric behaviors of the samples have been analyzed using dielectric permittivity, dissipation factor and electric modulus. (C) 2010 Elsevier B.V. All rights reserved.