Artificial and singular geochemical environments are created around the engineered barrier systems (EBS) designed to isolate high level nuclear wastes in deep geological repositories. A concrete-bentonite interface takes place within the EBS and it builds a significant chemical gradient (pH), approximately from pH 8 (bentonite) to pH 12 (low alkali concrete), in a few millimetre thickness. This disequilibrium triggers dissolution and precipitation reactions and form a thin altered region. In this area, poorly ordered authigenic clay minerals, mainly hydrated magnesium silicates, are formed adjacent to hydrated calcium silicates and calcite precipitates adhered to the interface with concrete. This paper presents the development of this authigenic mineral layer comparing 6–18 months to 13 years interfaces. Scanning Electron Microscopy with Energy Dispersive X-ray spectroscopy (SEM-EDX) morphological and chemical characterization with the aid of ternary plots, X-ray diffraction (XRD) and infrared (IR) data show the young to old interface evolution from single brucite layers to stevensite-saponite silicates composition. Geochemical calculations indicate that this layer acts as a pH~11 buffer useful to minimize bentonite alteration and to favour the retention of amphoteric metal ions.