In this work, mixed alkali borate glasses doped with Li2O were prepared with a molar composition of (75-x) B2O3-15Na2O-8CaO-1V2O5-1AgCl-xLi2O; x = 0, 5, 10, 15, and 20 mol% by using traditional melt-quenching process. X-ray diffraction studies confirmed the amorphous nature of the samples. Upon Li2O doping the glass density, measured at ambient temperature, increases from 2.336to 2.518 g/cm3, while molar volume decreases from 29.637 to 24.337 cm3/mol. The direct and indirect band gap energies determined using UV–Visible absorption analysis was in the range 3.000 –3.285 eV and 2.910–3.218 eV respectively. The DTA measurements indicated that with Li2O addition the thermal stability of the glasses has improved. FTIR study revealed the vibrational modes corresponding to the functional groups present in the glasses. The DC conductivity of the samples (measured at 588 K) was found to increase from 2.394 x 10-4 to 3.987 x 10-4 Ω-1m-1with Li2O content. The temperature dependency of DC conductivity followed Mott’s Small Polaron Hopping (SPH) model at high temperature and Variable Range Hopping (VRH) model at low temperatures. The linear fit of the data to the SPH model yielded the activation energy (W) values in the range 0.152 to 0.693 eV, whereas the density of states at Fermi level evaluated by the VRH model was in the order of 1030 eV-1m-3. The improved electrical conductivity of the prepared Li doped glasses together with their good thermal stability and transparency render them as potential candidates for optoelectronics device applications.