The effect of polyethylene glycol (PEG) and chloride ions on copper electrodeposits is investigated by electrochemical measurements (cyclic voltammetry, current and potential pulses) coupled with an ellipsometric study at open circuit. When PEG is added to the Cu2+ solution, the modifications of the copper electrodeposition mechanism can be explained by a polymer-electrode interaction instead of a complex formation in solution. Since ellipsometry has shown no PEG adsorption at least at open circuit, that adsorption is assumed to be potential dependent. Moreover, the efficiency of PEG alone in solution, seems to be decreased when the deposit grows. With Cl- alone, an activation of copper deposition is performed. The simultaneous addition of the two additives induces a blocking effect of the copper reduction that continues on with time. X-ray diffraction, optical microscopy and atomic force microscopy (AFM) carried out complementary results, on bulk deposits obtained from solution with and without these additives. It has been found that a bright, compact and homogeneous coating is only obtained in presence of both additives. In that case, the texture of the deposit is modified and the roughness is significantly decreased to 0.5 mum.