A novel process recycling Li from the spent LiFePO4 cathode material has been put forward. The new LiFePO4 sample is synthesized through hydrothermal reaction by using recovered Li3PO4 as Li source and FeSO4·7H2O as Fe source. The morphologies, structure and physicochemical properties of the re-synthesized LiFePO4 cathode material were characterized by Field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurement. The results showed that the morphology and particle size of re-synthesized LiFePO4 samples become more regular and smaller with the increase of the hydrothermal reaction temperature. Besides, it has been found that the LiFePO4 cathode material synthesized at 200 °C showed excellent electrochemical properties which deliver a high initial capacity of 144.25 mAh/g at the rate of 1 C and high capacity retention of 96.7% after 200 cycles. Therefore, this work provides a new strategy for recovery and recycle of the spent LiFePO4 cathode scraps.