The study of the microstructure of random heterogeneous materials, related to an electrochemical device, is relevant because their effective macroscopic properties, e.g., electrical or proton conductivity, are a function of their effective transport coefficients (ETC). The magnitude of ETC depends on the distribution and properties of the material phase. In this work, an algorithm is developed to generate stochastic two-phase (binary) image configurations with multiple geometries and polydispersed particle sizes. The recognizable geometry in the images is represented by the white phase dispersed and characterized by statistical descriptors (two-point and line-path correlation functions). Percolation is obtained for the geometries by identifying an infinite cluster to guarantee the connection between the edges of the microstructures. Finally, the finite volume method is used to determine the ETC. Agglomerate phase results show that the geometry with the highest local current distribution is the triangular geometry. In the matrix phase, the most significant results are obtained by circular geometry, while the lowest is obtained by the 3-sided polygon. The proposed methodology allows to establish criteria based on percolation and surface fraction to assure effective electrical conduction according to their geometric distribution; results provide an insight for the microstructure development with high projection to be used to improve the electrode of a Membrane Electrode Assembly (MEA).