A new preparation method for LiNiVO4 has been developed. LiNiVO4 can be readily obtained from the solid state reaction of LiNiO2 and V2O3 or V2O5 at 700 degrees C for 2 h in air. The quarternary Li-Ni-V-O reaction is strongly dependent on vanadium starting materials, reaction environment atmosphere, reactant stoichiometry and synthesis temperature. Individual particles of LiNiVO4 powders are well-formed crystallites shown clearly by scanning electron microscopy results to be in the shape of an octahedron. Powder X-ray diffraction studies of this crystalline material indicate that LiNiVO4 has an inverse spinel structure different from that of known cathode materials such as LT-LiCoO2 and LiMn2O4. The Li/LiNiVO4 cell can be charged and discharged at about 4.8 V versus metallic Li. To our knowledge, this is the Li intercalation reaction with the highest voltage known.