Abstract: Nickel is separated from copper contained in predominantly nickel- and copper-bearing sulphidic matte and alloys by chlorine leaching in an autoclave at over-atmospheric pressure. The leaching is conducted in an acidic solution at a redox potential range which favors the dissolution of nickel over copper. The obtained leach solution is purified in a cementation step carried out at atmospheric or over-atmospheric pressure by adding more sulphidic matte or alloy particles. The separated purified solution is treated for nickel recovery. Any cobalt present in the sulphidic matte or alloy reports with the nickel. Copper is recovered from the separated residue, which will also retain precious metals, if present.