The olivine polymorph LiCoPO4 was synthesized by solvothermal and a subsequent annealing process. Carbon free, ex-situ carbon coated and in-situ carbon coated materials were prepared. With the addition of citric acid in the solvothermal reaction, a carbon layer was coated via an in-situ approach. To systematically compare the different carbon coating routes, the structure and morphology of the LiCoPO4 materials were investigated by XRD, Raman, and SEM. HAADF-STEM combined with EDX was applied to analyze the homogeneity of the carbon layer and corresponding antisite defects. Electrochemical properties were analyzed by half-cells measuring cyclic-voltammograms, charge/discharge cycling behavior stability and rate-capability. It was found that the in-situ carbon coated LiCoPO4/C exhibited a superior electrochemical performance due to the relatively uniform and complete surface-layer formation. As a result, an appropriate carbon layer improves the electronic and ionic transport properties, ensures fast electron-transfer kinetics at the electrode particle surfaces and suppresses unwanted side reactions with the electrolyte.