Cations play a complex structural role in oxide glasses, as they occur in different kinds of environments, which allow them to exert a contrasted influence on physical and chemical properties of these glasses. The combination of structural information given by a wide range of spectroscopic methods and by radiation scattering, combined with numerical modelling, has given insight on the structural organisation around these cations. Among these characteristic properties are unusually low-coordination numbers, such as 5-fold coordination, and the presence of extended ordered domains, in which cation polyhedra are edge- or corner-sharing. This review presents evidence for a structural control of several physical and chemical properties in oxide multicomponent glasses. The use of zinc as a stabilising glass component arises from its network-forming position, which implies the presence of low-charge cations in its surrounding and as a consequence decreases the concentration of modifier components. The compositional dependence of glass coloration by transition elements has been investigated thoroughly through the example of nickel in silicate and borate glasses. The wide range of coloration observed may be explained by the existence of three kinds of environments, with nickel occurring in 4-, 5-, and 6- coordination. The relationships of these sites with the medium-range organisation of the glasses have been understood by a combined use of EXAFS spectroscopy and neutron scattering with isotopic substitution. The two other examples that are presented to illustrate structure–property relationships concern the physical solubility of gazes in glasses and the alteration processes of glasses used as analogues of nuclear waste matrices. In this last example, the use of structural probes as zirconium illustrates the influence of the alteration solution on the process of glass corrosion and further development of a gel at the glass–solution interface. A comparison with the evolution of the surrounding of iron shows that the two major processes, hydrolysis/condensation and dissolution/precipitation, depend on the element considered.
