The recovery of high-purity and high-value FePO4 raw materials from wastewater has great prospects in LiFePO4 battery industry due to the huge demand for new energy vehicle. However, the conventional in-situ FePO4 precipitation, as well as ex-situ PO43− adsorption-alkali regeneration, was incapable of efficiently obtaining high-purity products. To solve these problems, a dual-cycle regeneration method of Fe-NH2-polyacrylonitrile (PAN) adsorbent and H2SO4 desorbing solution was proposed to ex-situ FePO4 recovery from wastewater for Li-battery application. Benefitted from coordination interaction and electrostatic attraction, the maximum PO43− adsorption capacity of Fe-NH2-PAN reached 73.1 ± 0.4 mg/g. The average PO43− removal rate of continuous flow devices were 88.5% and 91.3% when treating low-P-concentration (0.22 mg/L) municipal wastewater (MW) and high-P-concentration (48.9 mg/L) slaughterhouse wastewater (SW) respectively. Furthermore, high-purity FePO4 analyzed by XRD spectra was achieved from the desorption solution at pH ∼1.6, resulting in the ultrahigh P recovery efficiencies of 91.4 ± 3.2%−96.3 ± 2.5% for SW and 82.7 ± 3.5% for MW. Besides, the LiFePO4/C electrodes made of recycled FePO4 exhibited a better discharge capacity (37.3−55.8 mAh/g) than that of commercial FePO4 agent (32.2−35.1 mAh/g) from 80 to 132 cycles, which showed the promising feasibility of recovering FePO4 from wastewater for Li-battery application.