In the context of temporary near-surface or reversible deep geological storage of intermediate-level radioactive waste (ILW), most wastes package concepts comprise an external container made of fiber reinforced concrete, receiving several primary waste packages. Self-irradiation of encapsulating and/or embedding matrices can lead to continuous production of hydrogen which, for obvious safety reasons, must be removed from the container. Previous studies have demonstrated that gas transport depends on two interdependent factors: the water saturation and the microstructural properties of the material. Most techniques used to investigate cement paste porosity require drying of the cement paste prior to the test, which can modify the material microstructure and does not permit the localization of the aqueous phase in the material with various degrees of saturations. This paper focuses on the characterization of pores in cement paste by thermoporometry. The technique, based on the thermodynamic conditions of the melting-solidification reactions of a condensate inside a porous body, provides a simple method for determining the pore size distribution in saturated cement pastes. The results obtained on cement pastes of different formulations with different types of cement are discussed in term of material microstructure and compared with those obtained by other techniques.