Electrochemical deposition of cationic and anionic polyelectrolyte on a Au electrode is studied as a function of applied potential between the electrode and the solution of monovalent electrolyte. The deposition is measured by open circuit potential relative to a pristine electrode in a reference solution (100 mM NaCl). The rate of deposition is measured by a home-built electrochemical-optical method in real time. It was discovered that the polarity of the potential and magnitude of the potential are not the primary reasons to enhance deposition. For example, both the amount and rate of deposition of negatively charged poly(styrenesulfonate) in NaCl are higher when the electrode is at -200 mV than at +200 mV with respect to the solution. The results are explained in terms of the charge state of the electrical double layer that is primarily controlled by supporting (small) ions.