In this work, peraluminous glasses (lack of alkaline and alkaline earth ions regarding aluminum) are under study to assess the potentiality of these matrices to confine fission products and minor actinides (FPA) at higher rate than current R7T7 glass (18,5 wt % FPA). The first part of this work aims at studying the physical and chemical properties of complex peraluminous glasses containing increasing FPA rate (18.5 to 32 wt %) to compare them with the specifications. The very low crystallization tendency of complex glasses containing up to 22.5 wt % as well as the very good chemical durability observed are major assets. The other part focuses on the lanthanides incorporation in simplified glass compositions in the SiO2-B2O3-Al2O3-Na2OCaO- Ln2O3 system (Ln = Nd or La). The glass homogeneity and devitrification tendency are investigated at different scales by XRD, SEM, TEM and structural techniques such as NMR (MAS, MQMAS, REDOR, HMQC, DHMQC) and neodymium optical spectroscopy that appear very powerful to determine the lanthanides structural role regarding aluminum and describe more precisely the structural organization of peraluminous network, as still unknown in such systems. The glass homogeneity was demonstrated in a large composition domain and new structural data were put in evidence at high lanthanides content.