Structural data have been obtained on the cation surroundings in multi-component silicate and borosilicate glasses using chemically selective spectroscopic and scattering methods, such as extended X-ray absorption and neutron scattering with isotope substitution (NSIS). Transition elements such as Ni or Ti may occur in unusual 5-coordinated sites which coexist with other coordination numbers, depending on glass composition. Distribution of cationic sites in the glassy structure is responsible for unusual spectroscopic properties, as shown by Fe2+ Mössbauer spectroscopy. The environment of cations such as Zn, Zr or Mo, has been determined by EXAFS and discussed using the bond valence theory, which predicts the way to charge compensate the oxygen neighbours and which indicates the linkage of cationic sites with the silicate framework. Cation-cation correlations are given by NSIS up to ∼8 Á, indicating an extensive Medium Range Ordering (MRO) with corner- and edge-linked cationic polyhedra, for Ti and Ni-bearing glasses, respectively. This heterogeneous cationic distribution in glasses is consistent with the presence of two-dimensional domains in which cation mixing may occur, as shown in a Ca-Ni metasilicate glass. Three-dimensional domains have also been found by Ni-K edge EXAFS in the case of low alkali borate glasses, with a local structure which mimics some aspects of crystalline NiO. The presence of ordered cationic domains, clearly illustrated by Reverse Monte Carlo simulations helps to rationalize the physical properties of multi-component silicate glasses.