An appropriate corrosion protection is required for transport and storage of high-quality goods and semi-finished parts made from metals. The application of volatile corrosion inhibitors (VCI) as a means of temporary corrosion protection is based on the release of corrosion inhibitors from films, papers, diffusers or oils to the gaseous phase. By adsorption on the metal surface, the inhibitors prevent the degradation of the primary oxide layer and hence impede corrosion. In principle, the anticorrosive effect is independent of the part geometry, because the protected surfaces are not in direct contact with the VCI material. Further, the VCI method does not require costly cleaning of parts prior to further use after transport and storage. A new approach for the evaluation of VCI is presented. A metallic sample is exposed in a chamber filled with air along with a VCI-containing product. In the course of the test, the air is humidified and the sample is then cooled down below the dew point, which leads to condensation of humidity. Electrochemical DC and AC methods, namely polarization resistance measurements and electrochemical impedance spectroscopy, are applied to characterize the state of the metallic surface under the condensed water film. The time-resolved analysis of the measurements provides a basis for the quantitative evaluation of the VCI's anticorrosive effect or a possible corrosion attack. The present work focusses on establishing the interrelations between the electrochemical response of the system and the test regime including initial exposition time of the dry sample along with the VCI in the test volume, the amount of VCI and the dwelling time of the sample under condensed humidity. The validity of the measurements is verified and the range of deviation is estimated. Exemplarily, the anticorrosive effect of various VCI-containing products on mild steel is evaluated. In summary, the presented application-oriented test is proven as a suitable method for the quantified assessment of VCI-containing products.