Antimicrobial gallium-doped phosphate-based glasses of general composition (P(2)O(5))(0.45)(CaO)(0.16)(Na(2)O)(0.39-x)(Ga(2)O(3))(x) (where x=0, 0.01, 0.03, and 0.05) have been studied using the advanced synchrotron-based techniques of Ga K-edge x-ray absorption spectroscopy and high-energy x-ray diffraction to provide a structural insight into their unique properties. The results show that the Ga(3+) ions are octahedrally coordinated. Furthermore, substitution of Na(2)O by Ga(2)O(3) strengthens the phosphate network structure because the presence of GaO(6) octahedra inhibits the migration of the remaining Na(+) ions. The results are discussed in terms of the use of Na(2)O-CaO-P(2)O(5) glasses as controlled-delivery devices for antimicrobial Ga(3+) ions in biomedical applications. We are thereby able to relate the atomic-scale environment of the Ga(3+) ions beneficially to the glass dissolution, and thus to their ability to disrupt bacterial cell activity by usurping the role of iron.