Fe2(SO4)3 solution was, for the first time ever, used as the leaching agent to leach Cu from malachite in this work. The results confirmed that malachite (Cu2(OH)2CO3) could be easily converted to water-soluble CuSO4 through a nearly stoichiometric reaction with Fe2(SO4)3 in the leaching solution and the leaching efficiency of Cu could reach ∼100% under the optimum conditions (the Fe3+/Cu molar ratio = 0.8, the liquid-to-solid ratio = 1–10 ml/g, the stirring speed = 300 rpm, and the leaching time = 120 min). This study provides a new hydrometallurgical method for the treatment of carbonate-type Cu ores such as malachite (Cu2(OH)2CO3) and azurite (Cu3(OH)2(CO3)2).