Some inevitable issues of the acid leaching method used to recycle spent lithium-ion batteries (LIBs), such as toxic gas emission, excessive acid-base consumption, inferior metal selectivity and equipment corrosion, have gradually emerged and restricted the promotion and development of this method. It is therefore essential to develop a sustainable closed-loop recycling technology (reduction-ammoniacal method) for spent LIBs. In this study, the effects of various species of ammonia, ammonium salts and reductants on the leaching of Li, Co, Ni, Mn and Al from spent LIBs were investigated with a hydrothermal method. An increase of the electrode potential of the reductant greatly accelerated the selective leaching of Li, Co and Ni, which agreed with the thermodynamic analysis results. The standard electrode potentials of the LiNiCoMnO (NCM) materials were also determined by using approximate calculations. When using (NH)SO as a reductant in a one-step leaching process, 100% Co, 98.3% Ni and 90.3% Li were extracted into the ammonia-ammonium chloride solutions. From the kinetics analysis, the surface chemical reaction shrinking core model was found to control the leaching behavior of Li, Co, and Ni in the reduction-ammoniacal leaching process. A shell-core structure was composed of a product layer, a diffusion layer of the solid core and an unreacted core. Species in the product layer reduced the leaching efficiencies of Li, Co, and Ni. The results obtained for this hydrothermal reduction-ammoniacal method applied to recycle spent LIBs provide insights for the design of a high-speed, exceptionally selective, closed-loop recycling technique.