The effect of Arsenic in copper-sulfate solutions during electrorefining of copper was investigated using scanning electron microscopy, X-ray diffraction and cyclic voltammetry analysis. Electrodeposition was carried out using Arsenic, Antimony and bismuth addition to sulfate electrolytes: 45 g/l $Cu^{2+}$ and 170 g/l $H_2SO_4$. Arsenic in sulfate electrolytes changed the morphology and structure of the copper deposits as compared with those obtained from impurity free solutions. When arsenic was present in the sulfate electrolytes, $Cu-3$As intermetallic phase was formed locally on the deposits.