Phosphate glass samples doped with silver ions through a Na+-Ag+ ion-exchange process were treated in a hydrogen atmosphere at temperatures near 430 °C for durations ranging from 4 to 5 h. Such treatment causes metallic silver precipitation at the surface as well as nanoclustering of silver atoms under the surface under conditions very similar to those used for silicate glasses. The presence of silver clusters resulted in a characteristic coloring of the glass and was verified by the observation of a plasmon resonance peak near 410-420 nm in the absorption spectra. Applying a DC voltage between 1.4 and 2 kV at temperatures between 120 and 130 °C led to dissolution of the clusters in the area under the positive electrode, thereby bleaching the glass color. The use of a patterned doped-silicon electrode further led to the formation of a 300 nm thick surface relief on the glass surface and of a volume complex permittivity grating extending at least 4 μm under the surface. Such volume complex refractive index gratings may find applications in passive or active (laser) photonic devices in rare-earth doped phosphate glasses, where conventional bulk grating formation techniques have limited applicability.