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The recycling of cathode materials for spent NCM has always been a major concern for the energy industry. However, among the current processing methods, the general leaching efficiency of Li is between 85% and 93%, with much room for improvement. The recovery of Ni, Co and Mn requires a high cost of secondary purification. In this study, to recycle the NCM cathode material, a route of sulphated reduction roasting – selective Li water leaching – efficiency acid leaching of Ni, Co, Mn – extraction separation – crystallisation was adopted. The results showed that after roasting (a temperature of 800 °C, a reaction time of 90 min, a carbon content of 26%, and a sulphuric acid addition of nH2SO4:nLi = 0.85), Li water leaching efficiency was 98.6%, followed by acid leaching of Ni, Co and Mn at around 99%. Mn, Co were extracted with Di-(2-ethylhexyl) phosphoric acid and 2-Ethylhexyl phosphonic acid mono-2-ethylhexyl ester respectively to obtain Ni, Co, Mn solutions, which eventually were crystallized for manganese sulphate, cobalt sulphate, lithium carbonate and nickel sulphate products, with high purity of 99.40%, 98.95%, 99.10%, and 99.95%. The results of this study improved the leaching efficiency of Li and were closely linked to the actual industrial preparation of Ni, Co and Mn sulphates, providing a feasible and promising basis for spent NCM cathode materials industrial recovery.