A new simple electrode based on a blended cathode as a practicable method for industrial application was introduced to improve the capacities of LiFePO4 cathodes. Here, the effects of physical blending with a small amount of Li3V2(PO4)3 on the electrochemical performance of LiFePO4 were studied. The influence of blended ratios on the capacity of LiFePO4 was examined by galvanostatic charge and discharge test. The results showed that the discharge capacity of LiFePO4/Li3V2(PO4)3 was increased from 146 mAh/g to 156 mAh/g by adding 20 wt.% Li3V2(PO4)3 and the mixture cathode exhibited excellent capacity retention (93.4% after 12 cycles) compared with prismatic ones. Moreover, the rate performance of LiFePO4 was also improved greatly by adding Li3V2(PO4)3. The beneficial effects of adding Li3V2(PO4)3 were found to be related to an improvement of the rate performance of LiFePO4 cathode, which was ascribed to the better electron conductivity of Li3V2(PO4)3.