The high temperature solid-state reaction between LiNiO2 and V2O3 (or V2O5) in air used to prepare LiNiVO4 has been further studied. This quarternary Li-Ni-V-O reaction is strongly dependent on reaction temperature and lithium stoichiometry in LixNi2-xO2 and has produced a highly crystalline LiNiVO4 material whose structure has been confirmed to be an inverse spinel by Rietveld analysis with a Bragg R-factor of 1.18 in the absence of crystal orientation preference. The cell performance of LiNiVO4 prepared at various temperatures or by varying x-values in LixNi2-xO2 has been examined in lithium coin cells and indicated that preparation at low temperatures or when x = 0.89 provided an electrode material with higher cell capacity.