Alteration of cement–bentonite interfaces and accompanying changes in diffusivity of tritiated water (HTO) was investigated experimentally using intact, hardened cement-paste specimens. The alteration by carbonate solution was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼70 ± 7%of the initial value after a 180-day period. Another alteration in contact with compacted bentonite was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼71 ± 10% of the initial value after a 600-day period. The changes in the diffusivity were considerably less than those observed for mixed specimens of ground, granulated hardened cement paste and bentonite where the diffusivity decreased to 20% of the initial value over 180 days. The results were extrapolated to 15 y under simple assumptions and showed good agreement with those observed in the cement–argillite interface at Tournemire URL (France). Such an explanation enhances confidence in the assessment of the alteration of cement-bentonite systems and might be a basis for using the data and models obtained in the long-term assessment of radioactive waste disposal.