LiV2O4, with spinel structure, is prepared under vacuum by heat-treatment of Li0.5VO2 obtained by chemical extraction of 0.5 lithium from the layered compound LiVO2. Similar treatment of Li0.465VO2 results in a cation-deficient spinel Li0.93V2O4. X-ray powder diffraction data show that LiV2O4 is only different slightly from Li0.93V2O4 The preliminary test of the experimental cell by using LiV2O4 as positive electrode is made.