Recycling of spent lithium-ion batteries has attracted wide attention because of their high content of valuable and hazardous metals. One of the difficulties for effective metal recovery is the separation of different metals from the solution after leaching. In this research, a full hydrometallurgical process is developed to selectively recover valuable metals (Ni, Co and Li) from cathode scrap of spent lithium ion batteries. By introducing ammonia-ammonium sulphate as the leaching solution and sodium sulphite as the reductant, the total selectivity of Ni, Co and Li in the first-step leaching solution is more than 98.6% while it for Mn is only 1.36%. In detail understanding of the selective leaching process is carried out by investigating the effects of parameters such as leaching reagent composition, leaching time (0–480min), agitation speed (200–700rpm), pulp density (10–50g/L) and temperature (323–353K). It was found that Mn is primarily reduced from Mn4+ into Mn2+ into the solution as Mn ( NH 3 ) x 2 + while it subsequently precipitates out into the residue in the form of (NH4)2Mn(SO3)2·H2O. Ni, Co and Li are leached and remain in the solution either as metallic ion or amine complexes. The optimised leaching conditions can be further obtained and the leaching kinetics is found to be chemical reaction control under current leaching conditions. As a result, this research is potentially beneficial for further optimisation of the spent lithium ion battery recycling process after incorporating with metal extraction from the leaching solution.