Abstract The microstructural stability or durability of a specific backfilling pozzolanic-cement mortar, which is employed in Spain, in concrete containers for the storage of low level liquid wastes (LLW) and medium level liquid wastes (MLW), has been studied by means of the Koch–Steinegger test at the temperatures of 20 and 40°C during a period of 365 days. Mortar samples were immersed in salt solutions of 3.46 M NaCl and 3.46 M KCl to simulate the salinity of some radioactive liquid waste matrices. The resistance of the mortar to the saline solution attack is evaluated by the development of the relative flexural strength. The changes of the microstructure were followed by mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Pore solution was extracted and analyzed at different periods of time to know the possible diffusion of sodium, chloride and potassium inside the microstructure.