This paper reports the results of microstructural analysis based on image analysis subjected to electrical current as a simulation of stray current effect. The purpose is to investigate the influence of electrical current flow on the development of microstructural properties in reinforced cement-based materials. In view of the significant contribution to material performance, the characterization of cement-based microstructure in an economical and reliable way is of high relevance to permeability prediction and durability studies of cement-based materials. In this study, taking the cement paste submerged in Ca(OH)₂ conditions as specimens, the pore size distribution and percolation was derived from image analysis of ESEM micrographs. The electrical properties of mortars were measured and their microstructural characteristics were investigated using quantitative image analysis techniques. Moreover this approach is compared with other general methods such as mercury intrusion porosimetry (MIP) and the comparison shows good consistency in development of parameters characterizing the materials' microstructure.