One of the main problems encountered by curators and conservators in charge of metallic collections from Historical Heritage is related to their long-term conservation, since metallic artifacts undergo corrosion phenomena, which are the result of the interaction between the metal and its environment. The use of rust converters and microcrystalline waxes can be an ecological alternative to the traditional and more aggressive conservation techniques. Although the mechanism of action of these compounds is not clear, it is assumed that they react with iron oxides and generate new compounds that may have a passivation effect on the metallic surface. This paper proposes to show how simple electrochemical techniques can be used as an efficient tool to contribute to the diagnosis of the conservation state of cannon balls and to monitor the restoration treatment. The objective of the present work is to evaluate the effectiveness of a rust converter based on tannins and phosphoric acid, and one microcrystalline wax applied on cannon balls samples exposed to a marine atmosphere. The protection properties of the oxide or conversion layer are evaluated by electrochemical impedance spectroscopy (EIS) technique. The results obtained suggest that the use of the rust converter and microcrystalline wax protects the cannon balls, even though its effect is less evident when the deterioration degree is larger.