A series of composite materials of general molecular formula (1 x) Na2SO4 (x) LDT was prepared by solid state reaction method. The phase structure and functionalization of these materials were defined by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) respectively. Differential thermal analysis (DTA) revealed that the hump of phase transition at 250 C has decreased while its thermal stability was enhanced. Scanning electron microscopy signifies the presence of improved rigid surfaces and interphases that are accountable for the high ionic conduction due to dispersion of LDT particles in the composite systems. Arrhenius plots of the conductance show the maximum conductivity, r = • 104 S cm1 at 500 C for the x = composition with the lowest activation energy eV in the temperature range of 573–773 K. The value of dielectric constant was decreased with increasing frequency and follows the usual trend. | Structural, electrical conductivity and dielectric behavior of Na2SO4–LDT composite solid electrolyte