This work presents the electrochemical behavior of Ag/AgCl electrodes (chloride sensors) in cement paste environment, monitored over a period of 180 days via open circuit potential (OCP) readings and electrochemical impedance spectroscopy (EIS). The EIS response indicates modification of the sensors’ morphology, in particular alteration of the AgCl layers, as a result of continuous chloride penetration into the bulk matrix towards the vicinity of the sensor/cement paste interface. A gradual shift to more cathodic OCP values and stabilization at approximately -1mVSCE to 2mVSCE was observed at the end of the test, reflecting chloride content of 820mM to 930mM in the pore solution surrounding the sensors, which differs 5-10% from the chloride concentration in the external solution. The water soluble chloride content in the cement pate, as destructively measured wet chemically by Volhard method and photometry, was in the range of 1100mM - 1300mM i.e. about 30-50% more than the chloride concentration in the external solution. This difference of maximum 50% in the recorded chloride levels is attributed to the fact that the sensors “read” the average amount of free chloride at the interface sensor/cement paste, while the destructively measured water soluble chloride reflects the average free (with possible contribution of physically bound chloride) in the total volume of analyzed cement paste. It can be concluded that for the conditions of this experiment, more reliable free chloride content is measured via the sensors’ readings. Hence, if chloride thresholds for corrosion initiation are to be determined, the sensors’ readings will be more representative and accurate if compared to destructive water soluble chloride determination.