Studies have been carried out on the dead roasting of a copper-iron and a copper-nickel-iron sulfide concentrate, followed by segregation roasting with coal and leaching with either curpric sulfate in aqueous acetonitrile or cupric chloride in brine solution to preferentially solubilize copper. The effect of dead roasting and segregation roasting conditions on the overall leaching of copper and the separation of copper from iron and iron and nickel is reported. An excellent separation of copper from iron and a good separation of copper from iron and nickel can be obtained provided sulfur is removed to 0.5 per cent or less during the dead roast and provided the coal addition and temperature of the segregation roast are near the minima required for the segregation of copper.