Meso- and micro-scale structural changes in matured hardened cement paste dried slowly for 1.5 years at different relative humidities (RHs) are evaluated by small-angle X-ray scattering profiles covering a q range of 0.017 nm− 1–30 nm− 1 with a fractal disc-shaped particle analysis and Guinier approximation. The fractal disc-shaped particle analysis revealed that calcium–silicate–hydrate (C–S–H) agglomerations are very thin (~ 2.5 nm) and of relatively large width (~ 35 nm) under high RH conditions. However, the agglomerations are segmented (in width) into ~ 10 nm below an RH of 40%. The Guinier approximation found the possibility that the scattering profiles in the range of 2 nm− 1–8 nm− 1 correspond to a spacing between C–S–H monolayers and it showed stepwise changes at 40%–50% RH. The stepwise behavior of the distance between C–S–H monolayers may explain a kink in water vapor desorption at around 40% RH.