Characterization of the Ag/AgCl electrode is a necessary step toward its application as a chloride sensor in a highly alkaline medium, such as concrete. The nucleation and growth of AgCl on Ag in 0.1 M HCl was verified through cyclic voltammetry. Ag anodization was performed at current densities, determined by potentiodynamic polarization in the same (0.1 M HCl) medium. The morphology and microstructure of the AgCl layers were evaluated via electron microscopy, while surface chemistry was studied through energy-dispersive spectroscopy and X-ray photoelectron spectroscopy. At current density above 2 mA/cm(2), the thickness and heterogeneity of the AgCl layer increased. In this condition, small AgCl particles formed in the immediate vicinity of the Ag substrate, subsequently weakening the bond strength of the Ag/AgCl interface. Silver oxide-based or carbon-based impurities were present on the surface of the sensor in amounts proportional to the thickness and heterogeneity of the AgCl layer. It is concluded that a well-defined link exists between the properties of the AgCl layer, the applied current density and the recorded overpotential during Ag anodization. The results can be used as a recommendation for preparation of chloride sensors with stable performance in cementitious materials.