A new extraction process suitable for treating refractory CuCo2S4 under atmospheric pressure acidic leaching conditions was investigated. The effect of variables such as oxidant species, liquid-to-solid ratio, leaching time, oxidizing agent and mineral quality ratio, H2SO4 concentration, temperature and sodium chloride concentration on the extraction efficiency of Co, Cu and Fe from CuCo2S4 were investigated. Under optimal conditions including P80-P90 of the sample was d < 0.0074 mm, stirring speed of 400 rpm, leaching time of 8 h with sodium chlorate (NaClO3) and mineral quality ratio of 0.5, 2 mol/L H2SO4, liquid-to-solid ratio of 7, leaching temperature of 90°C and 4 mol/L sodium chloride. The leaching efficiency of Co, Cu, and Fe were nearly 97.08%, 100%, and 92.45%, respectively. Furthermore, the contents of cobalt and copper in leaching residue were all less than 0.4 wt.%, which satisfies the requirements of industrial production.