Separation of copper and nickel by liquid-liquid extraction from aqueous solutions was studied using LIX 664N in kerosene as solvent. Both metals were taken in their sulfate form and ratio of copper to nickel in feed solutions was maintained as 10:1. LIX 664N concentration in kerosene was varied from 10% to 40% (v/v) and its effect was studied on percent extraction of copper and nickel for organic to aqueous (O:A) phase ratio of 2:1 at pH 2. Experimental results showed that at pH 2, copper was selectively extracted from its mixture with nickel. Selectivity for copper extraction was as high as 6000 with 40% LIX 664N. Calculations using extraction isotherm indicate almost complete recovery of copper in two stages with O:A ratio of 1:1 and in one stage with O:A ratio of 2:1. After extraction of copper, the pH of raffinate containing nickel was adjusted to a value of 9 by addition of ammonia solution. The effect of LIX 664N concentration on extraction of nickel was studied. Up to 80% nickel could be extracted with 30% LIX 664N at O:A phase ratio of 2:1. Stripping of copper from the organic phase with 180 g/l sulfuric acid at O:A phase ratio of 1:1 gave 98.5% copper recovery in a two-stage operation.