The structure of the glass 2MgO-2Al(2)O(3)-5SiO(2)-TiO(2) was investigated using neutron diffraction with isotopic substitution. Reverse Monte Carlo (RMC) modeling was used to reproduce experimental structure factors derived from diffraction experiments. The local environment of titanium atoms was determined and it corresponds to an average of 5.4 ± 0.2 oxygen atoms at a mean distance of 1.86 ± 0.02 Å. This coordination number agrees with the predominance of fivefold coordination, with the coexistence of four- and sixfold coordination in similar amounts. (27)Al nuclear magnetic resonance (NMR) results revealed that the proportion of highly coordinated aluminum atoms in this titanium-bearing glass was higher than in the titanium-free sample. RMC modeling was used to interpret the structural role of these ([5])Al species and we show a trend for preferential bonding between ([5])Al and Ti atoms. This favored linkage is important to understand the role of titanium dioxide as a nucleating agent in inorganic glass-ceramics fabrication.