The Raman spectra of AlCl3-LiCl-dimethylsulfone mixtures with different molar compositions have been recorded as a solid (300 K) and as a melt (400 K). In any case, only AlCl4- ion lines at 120, 179, and 347 cm(-1) were observed; we were unable to detect any other chloroaluminate species. Furthermore, some bands assigned to the Al[(CH3)(2)SO2](3+)(3) octahedral coordination compound are evidence for a high AlCl3 content.