It is of benefit for synthesizing and reusing process design of LiCoO2 to understand systemically the physicochemical property of LiCoO2 in the different conditions. In this paper, the mixture samples of LiCoO2 and NaHSO4稨2O with the molar ratio of 1:3, LiCoO2 and Na2S2O7 with the molar ratio of 1:1.5 were roasted. Occurrence evolution and distribution of elements in the sulfating roasting process of LiCoO2 have been studied by TG-DSC-MS, XRD, SEM and EDS. The results showed that reactions have been taken place in roasting. Occurrence of Na element is Na2SO4, LiNaSO4 and Na6Co(SO4)4. Occurrence of Li, Co element is LiNaSO4 and Na6Co(SO4)4 respectively in roasting products. The roasting products have a dense tissue and irregular shape. Distribution of Co element is homogeneous in the roasting products.