The solid-state reference electrodes made of polyaniline-coated MnO2 (SSRE-PAM) and their electrochemical characteristics were studied in simulated concrete pore solutions (SCPS) containing 0 and 3.5% NaCl. Saturated calomel electrodes (SCE) have been used to conduct electrochemical studies on the stability behavior of SSRE-PAM. Open circuit potential (OCP) and potentiodynamic polarization techniques were used to assess the corrosion performance of steel rebar exposed in SCPS with 0 and 3.5% NaCl using SSRE-PAM. The results demonstrate that the SSRE-PAM was capable of identifying steel rebar in a concrete environment that was either passive or active. Potentiodynamic polarization parameters such as Ecorr and Icorr for steel rebar in SCPS containing 0 and 3.5%)NaCl are greater than that of the passive condition (0% NaCl). All the studies validate the importance of using SSRE-PAM for corrosion monitoring applications in concrete structures.