The chemistry of the rechargeable system Li/LiAlCl4 . xSO(2)/C (where x = 2.8 to 6), which has an open-circuit voltage of 3.2 V, was investigated and compared with that of Li/LiGaCl4 . xSO(2)/C, which has an open-circuit voltage of 2.9 V. Cyclic voltammetry, pressure measurements, elemental analysis, and vibrational spectroscopy were used to monitor the cycling behavior and the nature of the discharge products. For the LiAlCl4 based electrolyte, the discharge products were LiCl and an amorphous complex believed to be (LiAlCl)-Cl-III(SO2)(3). For LiGaCl4 the solid discharge products were LiCl and a sulfur oxide species of the form SnO, where n is believed to be in the range of 6 to 10.