In this study, a multi-scale model called DuCOM (Durability COncrete Model), which is developed by the Concrete Laboratory at the University of Tokyo, is extended by coupling the geochemical code PHREEQC. The coupled numerical framework can address physicochemical and geochemical processes such as the hydration of cement particles, pore structure formation, multispecies transport, activity effect, thermodynamic reaction between aqueous solution and solids, etc. in cementitious materials, and therefore, it can potentially be used to assess the long-term durability of concrete structures. The model prediction for the composition of cement hydrates, pore solution chemistry, calcium profiles for the cement paste exposed in pure water, and calcium and sulphur profiles for the cement paste immersed in the sodium sulphate solution are qualitatively and quantitatively compared with experimental results obtained from literature. Finally, the importance of the strong coupling among various processes and mechanisms in the DuCOM-PHREEQC system is discussed.