Hedgehog-like LiCoPO4 with hierarchical microstructures is first synthesized via a simple solvothermal process in water–benzyl alcohol mixed solvent at 200°C. Morphology and crystalline structure of the samples are characterized by scanning electron microscope, transmission electron microscopy and X-ray diffraction. The hedgehog-like LiCoPO4 microstructures in the size of about 5–8μm are composed of large numbers of nanorods in diameter of ca. 40nm and length of ca. 1μm, which are coated with a carbon layer of ca. 8nm in thickness by in situ carbonization of glucose during the solvothermal reaction. As a 5V positive electrode material for rechargeable lithium battery, the hedgehog-like LiCoPO4 delivers an initial discharge capacity of 136mAhg−1 at 0.1C rate and retains its 91% after 50 cycles, showing much better electrochemical performances than sub-micrometer LiCoPO4 synthesized by conventional high-temperature solid-state reaction.