The behavior of steel reinforcement was studied using electrochemical impedance spectroscopy (EIS) and polarization resistance (PR) techniques in conditions of chloride-induced corrosion in ordinary Portland cement-mortar specimens immersed in 7% NaCl for a test period of 120 days and compared to specimens immersed in demineralized water for the same period as reference specimens. This study was an initial phase of ongoing research on electrochemical methods for corrosion protection in reinforced concrete structures and aimed at investigating the applicability of widely accepted techniques as EIS and PR and their possible correlation with structural observations of the bulk matrix, relevant to cement-based materials science and product-layers distribution, to corrosion and further protection. The results indicate that the concept of EIS modeling and the components used in the latter correspond well to alterations in structural properties of the bulk matrix, while the electrochemical behavior can be additionally supported by morphological observations of the steel/cement paste interface.