With the increasing consumption of lithium ion batteries (LIBs) in electric and electronic products, the recycling of spent LIBs has drawn significant attention due to their high potential of environmental impacts and waste of valuable resources. Among different types of spent LIBs, the difficulties for recycling spent LiFePO4 batteries rest on their relatively low extraction efficiency and recycling selectivity in which secondary waste is frequently generated. In this research, mechanochemical activation was developed to selectively recycle Fe and Li from cathode scrap of spent LiFePO4 batteries. By mechanochemical activation pretreatment and the diluted H3PO4 leaching solution, the leaching efficiency of Fe and Li can be significantly improved to be 97.67% and 94.29%, respectively. To understand the Fe and Li extraction process and the mechanochemical activation mechanisms, the effects of various parameters during Fe and Li recovery were comprehensively investigated, including activation time, cathode powder to additive mass ratio, acid concentration, the liquid-to-solid ratio, and leaching time. Subsequently, the metal ions after leaching can be recovered by selective precipitation. In the whole process, about 93.05% Fe and 82.55% Li could be recovered as FePO4 center dot 2H(2)O and Li3PO4, achieving selective recycling of metals for efficient use of resources from spent lithium ion batteries.