Poly (3,4-ethylenedioxythiophene), PEDOT, films were synthesized at room temperature by potentiodynamic and potentiostatic step deposition in aqueous solutions containing EDOT monomer and LiClO4. In some solutions, the effect of small amounts of sodium dodecylsulfate, SDS, on the polymerization rate of EDOT and on the stiffness of the obtained PEDOT film was studied. The obtained PEDOT films were transferred in aqueous solutions containing cations with different molar mass, such as H+, Li+, Na+, K+, and Cs+. The apparent molar masses of the exchanged species during potentiodynamic experiments were determined by in situ microgravimetry. These measurements underlined the importance of the electrolyte chosen for electropolymerization process. It is known that SDS anions can be trapped inside the polymer layer during electropolymerization, providing them with a cation exchange behavior. However, even if the PEDOT films were deposited from an electrolyte without SDS, they still acted as cation exchangers.