Copper and cobalt were extracted from nickel chloride solution with N235. The various parameters considered in this work were N235 concentration, reaction time, phase ratio (O/A) and pH value. The optimum conditions are determined that concentration of N235 in organic phase is 40% (volume fraction), the phase ratio (O/A) is 1:2, pH value is 2~4, chloride concentration is 5.76 mol/L and the reaction time is 4 min. Under the optimized operating conditions, cobalt and copper extracted effectively and the extraction rates at the single stage reached 90% and 97%, respectively. After five stage continuous counter-current process, the concentrations of copper, cobalt, iron in the raffinate are less than 0.0008 g/L，0.008 g/L and 0.0025 g/L, respectively, and the recovery of nickel is higher than 92%. The separation effect is steady and satisfied for the electrolysis.