Composite solid electrolytes in the system (1-x)Li2CO3-xAl2O3 with x = 0.1 – 0.6 mole were prepared via sol-gel technique. The morphology and conductivity of the composite were investigated. Obtained materials were analysed by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, Fourier transform infrared spectroscopy and chemical constituents were confirmed by energy dispersive X-ray. The ionic conductivity was measured using AC impedance spectroscopy. SEM studies of cross-section morphology clearly showed lithium carbonate crystals became radial – fluffy shaped particularly at x = 0.1 and 0.6. Morphological analysis showed homogeneous distribution between Li2CO3 and Al2O3 particles resulted in formation of amorphous phase of Li2CO3 at Li2CO3 - Al2O3 interface. Traces of α-LiAlO2, γ-LiAlO2 and LiAl5O8 were observed at x = 0.1, 0.2 and x = 0.4. Impedance spectroscopy studies showed that the conductivity is maximal at x = 0.2 and 0.4 - 0.5 with a value equal to ~10-3 Scm-1 with temperatures ranging from 130 - 180 oC.