Various LiFePO4 microstructures were synthesized via hydrothermal or solvothermal routes using different additives. In an aqueous solution, LiFePO4 spindles whose length was about 2 microm were obtained with the assistance of polyvinyl pyrrolidone (PVP). As PVP and P2O7(4-) added in water, ellipsoidal LiFePO4 particles which composed of nanoparticles around 100 nm in diameter were obtained. If the additive was cetyltrimethyl ammonium bromide (CTAB), sheet-like LiFePO4 crystals with the width of 100 nm were prepared. In the mixed solvents of water together with ethanol or acetylacetone, when adding CTAB or polyethylene glycol (20000), LiFePO4 plates or nanoparticles were obtained. The ellipsoidal LiFePO4 had the best electrochemical properties among all these products. It is found that the annealed samples were significantly better than the corresponding unannealed ones. Take the ellipsoidal LiFePO4 for example, the initial discharge capacity of annealed (161 mAh/g) was much higher than the unannealed ones (85 mAh/g) at 0.1 C and the former cell still could deliver a capacity of 143 mAh/g after 30 cycles.