The structural role of Gallium (Ga) is investigated when substituted for Zinc (Zn) in a 0.42SiO(2)-0.40-xZnO-0.10Na(2)O-0.08CaO glass series, (where x = 0.08). Each starting material was amorphous, and the network connectivity (NC) was calculated assuming Ga acts as both a network modifier (1.23), and also as a network former. Assuming a network forming role for Ga the NC increased with increasing Ga concentration throughout the glass series (Control 1.23, TGa-1 2.32 and TGa-2 3.00). X-ray photoelectron spectroscopy confirmed both composition and correlated NC predictions. Raman spectroscopy was employed to investigate Q-structure and found that a shift in wavenumbers occurred as the Ga concentration increased through the glass series, from 933, 951 to 960 cm(-1). Magic angle spinning nuclear magnetic resonance determined a chemical shift from -73, -75 to -77 ppm as the Ga concentration increased, supporting Raman data. These results suggest that Ga acts predominantly as a network former in this particular Zn-silicate system.