The submicron single crystals of LiCoPO4 with 500 nm diameter are prepared by solvothermal method. The carbon coated sample is obtained using sucrose as carbon source under 650 °C subsequently. It is investigated that the solvent composition has an effect on the morphology and the electrochemical performance of the cathode material. The as-prepared samples are characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopic, dynamic light scattering, and Fourier transform infrared spectra. The electrochemical performance is evaluated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The LiCoPO4/C cathode can reach an initial discharge capacity of 123.8 mA h g−1 at 0.1C, with a retention of 83% after 100 cycles. A discharge capacity of 84.9 mA h g−1 is still attainable when the rate is up to 2C. The good cycling performance and rate capability are contributed to the decrease of particle size along with the lower antisite defect concentration in the LCP crystals, and uniform carbon coating.