Assessing the long-term behavior of nuclear glass implies the prediction of their long-term performance, and more precisely of their evolution under irradiation and during interaction with water. After briefly recalling the major characteristics of the local and medium-range structure of borosilicate glasses of nuclear interest, we will present some structural features observed under forcing conditions. Specific structural tools (EXAFS/XANES, Neutron/x-ray diffraction, solid state spectroscopic methods…) are correlated with numerical simulations to determine the local structure of glass and provide selective information on glass surface using total electron yield detection. During alteration in near- or under-saturated conditions, some elements such as Fe change coordination, as other elements such as Zr only suffer structural modifications in under-saturated conditions. These structural modifications may explain the chemical dependence of the initial alteration rate and the transition to the residual regime. They also illustrate the molecular-scale origin of the processes at the origin of the glass-to-gel transformation. Molecular scale processes help in predicting the properties of new generations of nuclear glasses required by future production of nuclear energy. Under irradiation, various structural effects are observed, including coordination change, ion migration or disorder effects. These studies show that glasses with a simplified composition do not show the same behavior as more realistic glasses. Molecular dynamics (MD) simulations provide complementary information on elastic effects. Recent direct evidence for B-coordination change under external irradiation together with structural models derived from MD sheds light on the structural mechanisms at the origin of radiation-induced modifications of glass properties, emphasizing the importance of the thermal regime in the cascade core.