The conductivity of 1.8 M LiAlCl4/SOCl2 electrolyte solutions showed the greatest temperature dependence at 298 K. Raman spectra results suggest that the adduct compound is Li(SOCl2)(y-x)(SO2)(x)(+). The structural changes in LiAlCl4/SOCl2 electrolyte solutions were analyzed using Li-7 NMR spectroscopy. The Li-7 spin-lattice relaxation rate indicated a change in the ionic structure of the electrolyte near 295 K which was confirmed by measuring the chemical shifts and relaxation times under Various temperatures and concentrations. The concentration effects on conductivity of LiAlC4/SOCl2 electrolytes were also investigated. All experimental results suggest that the transition phenomenon in LiAlCl4/SOCl2 electrolyte solutions is related to the transformation between Li(SOCl2)(y-x)(SO2)(x)(+) and Li(SOCl2)(y)(+).