Lithium samariumsilicate (LSS) was synthesized using a sol-gel process. The formation of crystalline phase and structure of the LSS compound were obtained by monitoring the dried gel heat treated, at various temperatures, from amorphous to crystalline growth through XRD and FTIR measurements. Bulk conductivity of the LSS sample was calculated from the analyzed impedance data, at different temperatures, using Boukamp equivalent circuit software. The activation energy (E-a) obtained from the slope of log sigma T versus 1000T(-1) was 0.55 eV. ac conductivity was calculated using the measured impedance data at different temperatures and it was analyzed using Jonscher's Universal Power Law (JUP). The evaluated power law exponent s exhibits a non-linear behavior with temperature. The ion relaxation behavior was explained with the diffusion controlled relaxation model. Electric modulus (M* = M' + iM'') was calculated from impedance data, which exhibits non-Lorentzian type peak with a relaxation frequency, omega(o), and a tail extending in the region of shorter relaxation time. The peak frequency omega(o) shifts towards the higher frequency with increase in temperature. (c) 2005 Elsevier B.V. All rights reserved.