The combined effects of carbonation and chloride attack can accelerate the degradation of reinforced concrete (RC) structures. In this study, the effect of natural carbonation on the chloride binding behaviours in Ordinary Portland cement (OPC) paste was investigated. The phase-equilibrium model for the dissolution/precipitation reactions and the surface complexation model for the ionic adsorption of C–S–H were adopted. An experiment from the literature was used as the benchmark. The results indicate that Kuzel's salt is produced when OPC paste is exposed to a mild chloride attack. During the natural carbonation process, Kuzel's salt is converted into Friedel's salt. As the carbonation continues, the Friedel's salt disappears. Complete natural carbonation results in a total loss of chemical binding capacity, and only a partial loss of the physical binding capacity in cement-based materials. This completely differs from the accelerated carbonation commonly used in the laboratory, which can cause complete loss of both chemical and physical binding capacity. Therefore, the durability design of RC structures vulnerable to the combined attack of chloride and carbonation based on the results of the accelerated carbonation is conservative.