The present study describes a method for the determination of As (III) and As (V) in copper electrolytes. The method is based on the separation of As (III) from a copper electrolyte by triple liquid-liquid extraction using a non-polar organic solvent in a medium of 10-12 mol L–1 HCl. The extract contains As (III) and the raffinate-As (V), respectively. As(III) specie can be re-extracted from the organic solvent through the water. Analyzes of the concentration of As in the re-extract and raffinate were performed by ICP-OES spectroscopic method. The average recovery of arsenic by the proposed method is about 99%. Repeatability was estimated with RSD (n = 6). Selectivity and accuracy were proven by the standard addition method. The relative error for restoring the standard addition of As (III) is about 0.3%. The speciation method analysis could be applied for determination of the arsenic species in the analytical quality control of refined copper in copper tanks in the production of copper cathodes.