Abstract Coupled water and chloride transport in cement mortar is analyzed experimentally in the paper. Samples with initial moisture content corresponding to 45% relative humidity are subjected to one-sided sodium chloride-in-water solution uptake, and moisture profiles and chloride concentration profiles are determined in three chosen time intervals. In the evaluation of measured moisture profiles and chloride concentration profiles, diffusion model is employed. Moisture diffusivity is determined as function of moisture content and chloride diffusion coefficient as function of chloride concentration using two methods commonly used for analysis of moisture profiles, namely the double integration method and the Matano method. The highest values of both coefficients are obtained by Matano method for the curves corresponding to 24 h exposure to the solution, the lowest values by Matano method for 168 h, the results obtained by double integration method are in between. The complementary experiments with distilled water as penetrating liquid performed for the sake of comparison do not show this feature. It is observed that water transport in the initial time period is for the chloride solution faster and in later times slower than for distilled water. Therefore, the observed differences in the calculated apparent values of moisture diffusivity and chloride concentration coefficients are attributed to the fact that Cl− and Na+ ions are adsorbed on the pore walls faster than water molecules. This effect should be included into the mathematical models using ion binding isotherms.