Abstract: A large number of spent refractory materialsis produced after overhaul of aluminum reduction cells. The XRD and composition of spent refractory materials was analysed, and dissolution experiments were studied in laboratory. The results show that the spent refractory materials is mainly consists of nepheline and flourides, and the leaching solution is alkaline. The concentration of fluoride ion in leaching solution is much higher indicating the main hazards of spent refractory materials is the soluble fluorides. The advantages and disadvantages of existing treatment methods of spent refractory materials are analyzed. The vacuum reduction and distillation process can not only recover fluoride electrolyte and sodium, but also regenerate refractory materials. It can recover all components of spent refractory materials with non-polluting and economic benefits.