Li2WO4-LiI-Al2O3 solid electrolytes have been found to be a potential electrolyte for battery applications due to its high electrical conductivity at ambient temperature. The binary solid electrolyte with incorporation Al2O3 was prepared in solid state reaction and characterized by Electrical Impedance Spectroscopy (EIS) and 7Li Magic Angle Spinning (MAS) solid state Nuclear Magnetic Resonance (ssNMR) technique. Maximum electrical conductivity of 3.35x10-3 Scm-1 was recorded for the sample containing 20 wt.% of LiI. The conductivity improved up to 3.92x10-3Scm-1 as 5wt.% of Al2O3 was added into the optimum composition of the binary system. Mobility of the charge carrier in the sample was investigated and NMR result showed that the electrolyte with high ionic mobility contribute into high electrical conductivity.