The electrochemical response of Prussian Blue films in NaCl solutions was studied. It was proved that the stability with cycling of PB films increased when these films are covered with a Nafion® membrane. This fact allows PB films to be studied in NaCl solutions under steady state conditions by impedance spectroscopy and ac-electrogravimetry. A model, which can explain the differences between the electrochemical behaviour of amorphous PB films and crystalline PB films in NaCl solutions, is proposed. This model is based on the hypothesis of a partial dehydration of the sodium ions before the electrochemical reactions take place, allowing the transport of sodium ions through the zeolitic channels of Prussian Blue.