A method of winning copper and accompanying metals from a copper-containing material selected from the group consisting of sulfidic ores or their concentrates, post-flotation deposits and waste products from pyrometallurgical processing of copper ores, which comprises grinding the material to a particle size below 0.1 mm., leaching the resulting comminuted material with a solvent system comprising a mixture of a heterocyclic aromatic amine selected from the group consisting of pyridine, .alpha.-picoline, .beta.-picoline, .gamma.-picoline and 2,6-lutidine, with a chlorinated methane derivative selected from the group consisting of methyl chloride, methylene dichloride, chloroform and carbon tetrachloride, whereby insoluble values of the metals are dissolved in the resulting solution due to the formation of a soluble metal-chloro- amine complex, filtering the solid residue from the resulting solution and separating the metal compounds from the organic phase, and recovering the metals by electrowinning.