The charge-transfer reaction between copper(II) and copper electrodes is studied in electrolytes that are similar to galvanic copper baths, 2.2 M H2SO4 + 0.3 M CuSO4 + chloride ions (c(Cl) less than or equal to 1 x 10(-2) M), and polyethyleneglycol 1500 (PEG, c(PEG) less than or equal to 4 x 10(-3) M). Electrochemical quartz crystal microbalance (EQCM) measurements are conducted, mainly under conditions of cyclic voltammetry. The formation and dissolution of CuCl on the electrode surface at c(Cl) greater than or equal to 2 mM is demonstrated, a notable shift of the pseudo-equilibrium potential associated with CuCl deposition is analyzed, and the inhibition of the charge-transfer reaction by the PEG/Cl- surface layer is characterized. It is shown that the inhibiting layer forms by reaction between the adsorbate-covered copper electrode and PEG, i.e., neither Cu+ nor Cu++ from the electrolyte are required. Numerical simulations of the processes as well as parallel experiments conducted with electrolytes not containing Cu(II) support the proposed mechanisms, in particular the role of the intermediate Cu+. (C) 2003 The Electrochemical Society.