New nuclear highly durable glass compositions, able to immobilize a higher concentration of high-level nuclear wastes than current borosilicate nuclear glasses, are being studied. Investigations are performed on rare earth (RE)-rich glasses, known as durable matrices. After a preliminary study on complex and simplified compositions, a basic glass composition was selected and studied (wt%): 51.0 SiO2-8.5 B2O3-12.2 Na2O-4.3 Al2O3-4.8 CaO-3.2 ZrO2-16.0 RE2O3. Chemical durability, physical properties (viscosity, transformation temperature), and crystallization tendency of glasses containing either a mixture of RE (La + Ce + Pr + Nd) or only one RE were studied and compared. The local environment of RE (for RE = Nd) in the glass and its evolution according to Nd2O3 concentration (from 1.3 to 30 wt%) was also studied by coupling characterization methods such as extended X-ray absorption fine structure spectroscopy at the neodymium LIII-edge and optical absorption spectroscopy. 11B, 27Al magic angle spinning-nuclear magnetic resonance, and Raman spectroscopy were also used to study glass structure.