Li2O-B2O3 composite gels were successfully prepared from tri-n-butyl borate and lithium methoxide dissolved in methanol and tetrahydrofuran via sol-gel technique. Sol-gel process, micro-morphology, ingredient of the gel samples were characterized by viscosity analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, transmittance electron microscopy and infra-red spectrum analysis. The results indicate that raw gel are dried after 4 h at 150 ℃ and crystallization is observed in the xerogels. Micro-morphology of Li2O-B2O3 composite gels will transfer from non-crystal to crystal at about 492 ℃, and the crystal liquates at about 808 ℃. The obtained dry gels are materials with porous configuration. The gel network appears to be composed of primary units l