To efficiently co-extract Ni and Cu from low-grade nickel-copper sulfide ore, chlorination roasting with NH₄Cl followed by a water leaching process was investigated. The results show that 98.4% Ni and 98.5% Cu can be synchronously extracted when the ore particle size is 75-80 μm, the roasting time is 2 h, the mass ratio of NH₄Cl to ore is 1.6:1 and the roasting temperature is 550 °C. The evolution behavior of various minerals was elucidated using X-ray diffraction (XRD) coupled with scanning electron microscopy (SEM). The kinetics of the chlorination process based on the differential thermal and thermogravimetric analysis (DTA-TG) data was analyzed by Kissinger method and Flynn-Wall-Ozawa (FWO) method. The chlorination process of low-grade nickel-copper sulfide ore mainly contains two stages: the decomposition of NH₄Cl and the chlorination of ore. The maximum apparent activation energies (E_a) at two stages are determined to be 114.8 and 144.6 kJ/mol, respectively. The condensed product of exhaust gas is determined to be ammonium chloride, which can be recycled as the reactant again, making the process economic and clean.