Preparation of LiCoPO4 platelets by simple microwave-assisted solvothermal process. Influence of solvent on morphology and electrochemical performance is investigated. Co-solvent plays a key role in tuning the size, shape and orientation of crystals. LiCoPO4 from triethylene glycol co-solvent shows best electrochemical performance. Discharge capacity of 141 mAh g−1 and energy density of 677 Wh kg−1 are reached.