3-Mercapto-1-propane sodium sulfonate (MPS), diaryl-dimethyl-ammonium-chloride (DDAC) and Cl- were used as additives for copper foils electrodeposition. First, we made copper foils with several combinations of additives, and evaluated surface smoothness, surface morphology and crystallographic structure by laser microscopy, field emission scanning electron microscopy and X-ray diffraction measurement. We found that the copper foil prepared with a bath containing all kinds of additives has the smoothest surface, the finest size in the crystal grains and the strong (111) orientation. Second, we examined the behavior of the additives by the Quarts Crystal Microbalance (QCM) measurement and the electrochemical measurement. Due to the weight increase by the QCM with electrolytes containing MPS and DDAC. Inhibitation effect was also observed by the electrochemical measurements with electrolytes containing DDAC.