In this work, a solid-state field-assisted diffusion technique is used to induce diffusion of silver or gold ions into a silica matrix. The obtained systems are characterized by secondary ion mass spectrometry and Rutherford backscattering spectrometry. The metal/glass interface chemistry plays an important role in the behavior of the metals and, especially for Ag, a proper time is required for the deposited film to first oxidize and then diffuse into the matrix, owing to the external electric field. Diffusion of Ag in silica is observed to be very sensitive to the applied field at relatively high temperatures, being stopped when a high field value is applied. This behavior may be attributed to the low availability of sites and the build-up...