The passivity behavior of copper anode containing impurities in copper sulfate solution for electrorefining process was studied at several different levels of impurities such as As, Sb, Bi and Pb. The passivity behavior was investigated by electrochemical techniques (galvanostatic, potentiodynamic and cyclic voltammetry tests) and surface analysis (optical microscopy, electron probe microanalysis, scanning electron microscopy). The results were that arsenic, antimony inhibited passivation and bismuth accelerated it and lead containing anode showed different passivity behavior from above anodes. The improved passivity characteristics could be explained by decrease in oxygen content in passivity film which resulted from a reaction among the impurities, oxygen and copper in the anode. The SEM image revealed that arsenic or antimony containing anode exhibited a porous passivity film and bismuth containing anode showed the compact passivity film and lead containing anode had loose passivity film on anode.