Abstract Addition of LiBO2 glass which acts as sintering aid is carried in Li3.6Si0.6V0.4O4 (LVSO) sample. The solid electrolyte is synthesized using conventional solid state sintering. LiBO2 is added with an aim to enhance the ionic conductivity of LVSO system for solid state Li+ ion battery applications. X-ray diffraction is studied for all samples. Addition of LiBO2 in LVSO makes denser pellet which is revealed by SEM. Compositional analysis is done using EDS which confirms that proper stoichiometry is maintained. Conductivity of LVSO electrolyte increases with addition of lithium borate glass. It can be attributed to decrease in porosity of ceramic in glass added samples. Highest ionic conductivity of 6.4 × 10−4 S cm−1 at 423 K is observed for 2 wt% LiBO2 addition with lowest activation energy of 0.43 eV. Transport number measurement is carried out which confirms Li+ ion conduction. IR spectra are studied to know the structural groups present in the ceramics.