Abstract: Alteration experiments have been performed using RTT7 and synthetic basaltic glasses in MgCl2-CaCl2 salt solution at 190°C. The duration of experiments ranged from 0.25 to 463 days. The alteration products were studied by Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD) and Electron Spectrometry for Chemical Analysis (ESCA). For both glasses, the early alteration product is a hydrotalcite-like compound [Mg6Al2CO3(OH)16·4H2O] in which HPO42−, SO42− and Cl− substitutes for CO32−. The measured basal spacing is 7.68 Å for the hydrotalcite formed from R7T7 glass and 7.62 Å for the hydrotalcite formed from basaltic glass which reflect the high Al/Al + Mg ratios x (0.34 ≤ x ≤ 0.46). The chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after a few months. These results support the use of basaltic glasses alteration patterns in Mg-rich solution, to understand the long-term behavior of R7T7 nuclear waste glass.