Abstract: The mechanism of LiCo1-xNixO2(x=0, 0.5, 1) synthesis from carbonates or hydrates was studied by thermogravimetric analysis and X-ray diffraction to identify the medium and final products. The synthesis process from carbonates can be divided into two steps. Below 300℃cobalt carbonate and/or nickel carbonate decompose forming oxides. Over 300℃ Li2CO3 decomposes and reacts with Co and/or Ni oxides gradually, as a result Co++ and/or Ni++ areoxidized to Co+++ and/or Ni+++, finally LiCo1-xNixO2 forms. The proportion of cobalt tonickel in the starting mixture and atmosphere during synthesis affects the structure of products.LiCo1-xNixO2(x≤0.5) can be synthesized in air or oxygen and characterized by solid solutionof LiCoO2 and LiNiO2. LiNiO2 can be obtained only from hydrates and in oxygen atmosphere.LiNiOz and LiCo0.5Ni0.5O2 have higher first charge capacity than that of LiCoO2. Their discharge capacity reaches a level with that of LiCoO2 and has reasonable reversibility.