A new kind of citric acid complex method has been developed in this study for synthesizing inverse spinel LiNiVO4 powder which can be used as the cathode active materials for lithium ion batteries with a very high voltage (4.8V versus Li). Li2CO3, NiCO3 and NH4VO3 were used as raw materials, and citric acid was used as a complex agent. Fine LiNiVO4 powders with particle size 0.5μm or less were successfully prepared at 500°C in 1h. Compared to the conventional solid state reaction methods, the citric acid complex method greatly reduced the temperature and the time for preparing pure LiNiVO4. The resulting LiNiVO4 powders were also characterized by TGA, XRD, SEM, IR and ICP techniques.