Composite solid electrolytes in the system (1-x)Li2CO3-xAl2O3, where x = 0.1–0.7 were prepared by sol gel method using lithium carbonate and aluminum oxide precursors in ethanol. The gels obtained due to the addition of citric acid were calcined at 80 and 100 oC. Their structural, thermodynamic and electrical properties were investigated by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and impedance spectroscopy. The results indicated that interface phases of crystalline and amorphous exist in this composite system of (1-x)Li2CO3-xAl2O3. The presence of the interface phases are due to the chemical and physical interactions between both crystalline Li2CO3 and Al2O3. The Arrhenius plot of the composite system showed non-linear curves and reached maximum values of ∼10−4 - 10−5 S cm-1 at 150 -180 °C. Based on the results of this study, it can be concluded that the sol gel method used in the preparation of the composite system, has an important role to crystal morphology changes that results in high ionic conductivity.