A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H2O2 amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li2CO3 with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB.