The level of degradation of reinforced concrete bridges was evaluated based on the in-situ measurements performed on five reinforced concrete bridges under service located in the Czech Republic. The combined effect of carbonation and chlorides with respect to the corrosion of steel reinforcement, namely the pH and the amount of water-soluble chlorides, were evaluated on drilled core samples of concrete. Based on these parameters, the ratio between the concentrations of Cl– and OH, which indicates the ability of concrete to protect reinforcement, was calculated. All the data were statistically summarized and the relationships among them were provided. The main goal of this study is to evaluate the non-proportional effect of the amount of chlorides per mass of concrete on the risk of corrosion initiation and to localize the “critical” locations in the bridges that are the most affected by the degradation effects.