This contribution couples (a) Small angle X‐ray scattering (SAXS) experiments of a high‐performance concrete (HPC) at the millimetric scale, and (b) Focused ion beam/scanning electron microscopy (FIB/SEM) of the cement paste of the HPC, with 10‐20 nm voxel size. The aim is to improve the understanding of the 3D pore network of the HPC at the mesoscale (tens of nm), which is relevant for fluid transport. The mature HPC is an industrial concrete, based on pure Portland CEMI cement, and planned for use as structural elements for deep underground nuclear waste storage. Small angle X‐ray scattering patterns are computed from the 3D pore images given by FIB/SEM (volumes of 61‐118 μm3). They are positively correlated with SAXS measurements (volumes of 5 mm3). Aside from correlations with FIB/SEM data, experimental SAXS allows to investigate a wider range of effects on the pore structure. These are mainly the HPC drying state, the presence of aggregates (by analyzing data on cement paste alone), and the use of Poly Methyl MethAcrylate resin impregnation.