Cathode material LiCoPO₄ was synthesized by solvothermal method with a variety of water/alcohol solvent mixtures, including ethanol (ET), ethylene glycol (EG), and diethylene glycol (DEG). Focus of this work was set on the effect of the different alcohol solvent on morphology and particle size of material. Composition, crystal structure, morphology and particle size of the as-prepared samples were characterized by X-ray-diffraction, scanning electron microscopy and specific surface area test. The results show that relationship of the average particle size of the LiCoPO₄ samples synthesized with different alcohols solvents is in agreement with solubility of solvent for the precursor, but is inconsistent with the viscosity of solvent. Furthermore, LiCoPO₄ sample synthesized with EG/H₂O possesses the smallest particle size, great crystallinity and excellent cycle performance. Its initial discharge specific capacities reaches to 130 mAh/g at 0.05C, and it shows a capacity retention of the initial value of 88% in 20th cycle. A variety of shapes are obtained from various co-solvents: hexagonal platelets for LiCoPO₄ obtained from EG, whereas, square platelets for LiCoPO₄ from ET/H₂O and DEG/H₂O.