This work refers to the application of a Voltammetric Anodic Dissolution (VAD) Technique in the analysis of coating discontinuities, focusing on pores and cracks that exposed the substrate. An evaluation was made of the influence of several parameters, such as the concentration of the passivation solution and sweep rate (SR), on the substrate passivation process and on the porosity indexes of tricationic phosphate coatings of Fe/Zn/Mn. The phosphatization process used was a commercial tricationic Fe/Zn/Mn phosphate bath applied on a galvanized steel (GS) substrate. Once the best experimental conditions for the use of the VAD technique had been defined, the grain size and layer weight were related to porosity indexes. The porosity was found to show a tendency to decrease with increasing grain size. The VAD technique consists of the anodic polarization of the substrate/coating system and measurement of the charge density involved in the substrate passivation process. A quantitative porosity index was obtained by comparing the passivation charge density of the substrate without coating (standard passivation charge density) and the passivation charge of the coated substrate.