Moisture and ionic transport under non-saturated condition is an important, but poorly understood transport phenomena particularly for mature systems containing supplementary cementitious materials. This paper investigates the moisture and chloride profiles of 3-year old mortars containing Portland cement (OPC), slag and silica fume (SF) after long-term (30–48 months) wick action exposure in 1.09 M NaCl solution. Moisture profiles were measured with 1H NMR relaxometry and chloride profiles with microXRF. The measured profiles were discussed in relation to moisture dependent material properties such as chloride diffusion coefficients, moisture diffusion coefficients, and desorption isotherms. Results show that the combination of different cementitious materials, e.g. the cementitious binder, is the key factor affecting chloride penetration depth. The cementitious binder also strongly affects chloride diffusion coefficient, moisture diffusion coefficient and chloride binding properties, which are all important parameters for the prediction of chloride ingress.