The recycling of spent LiFePO4 batteries has received extensive attention due to its environmental impact and economic benefit. In the pretreatment process of spent LiFePO4 batteries, the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality. In this work, a facile and efficient pretreatment process is first proposed. After only freezing the electrode pieces and immersing them in boiling water, LiFePO4 materials were peeled from the Al foil. Then, after roasting under an inert atmosphere and sieving, all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils. The active materials were subjected to acid leaching, and the leaching solution was further used to prepare FePO4 and Li2CO3. Finally, the battery-grade FePO4 and Li2CO3 were used to re-synthesize LiFePO4/C via the carbon thermal reduction method. The discharge capacities of re-synthesized LiFePO4/C cathode were 144.2, 139.0, 133.2, 125.5, and 110.5 mA·h·g?1 at rates of 0.1, 0.5, 1, 2, and 5 C, which satisfies the requirement for middle-end LiFePO4 batteries. The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.