Bleed stream from electro refining step of copper smelter was processed to recover the metals as high value products such as copper and nickel powders or salts. The process consists of partial decopperisation of the bleed stream followed by crystallization of a mixed salt of copper and nickel sulphate, leaching of the mixed salt, removal of iron, solvent extraction for the separation of copper and nickel and winning the solution to produce metal powders. After partial decopperisation of copper bleed stream, the resultant solution was subjected to crystallization which produces composite crystals with the chemical composition of 8.4-12.5% Cu, 13.7-14.38% Ni and 1-2 ppm of Fe as impurity. This mixed salt was leached with water and was treated for iron precipitation. The purified solution was subjected to solvent extraction using two solvents namely LIX 84 or Cyanex 272. A 20% LIX 84 in kerosene extracted 99.9% copper and 0.059% nickel at a pH of 2.5, similarly a 5% Cyanex 272 in kerosene extracted 98.06% copper and 0.51% nickel at a pH of 4.85. LIX 84 was used for metal separation in the mixer-settler unit and a flow sheet was developed using this solvent. The pure solutions of copper after stripping it from the loaded organic and nickel left in the raffinate were further electrolysed to produce pure copper (99.9%) and nickel (99.8%) powders, alternatively pure sulphate salts could also be crystallized. Since it is well known that Cyanex 272 is used for the separation of cobalt and nickel, a few experiments were performed on the extraction of copper by using Cyanex 272. A complete study is yet to be done to develop a flow sheet by using this solvent. (C) 2008 Elsevier Ltd. All rights reserved.