Improvement in the rate properties of orthorhombic LiVOPO4 was investigated and it was found that making a fine powder of LiVOPO4 by the mechanical milling pretreatment is effective for increasing the de-intercalation capacity of Li from LiVOPO4. The electrochemical de-intercalation capacity at high current density can further increase by optimizing the acetylene black amount as a conducting binder. The optimized acetylene black amount was 15wt.% and intercalation capacity of Li was achieved a value of 100 and 60mAhg−1 at high rate condition of C/5 (0.4mAcm−2) and 1C (2mAcm−2), respectively.