Photocatalytic glass-ceramics doped with metallic Ag, semiconductor AgBr, and hybrid metal-semiconductor Ag-AgBr nanostructures were synthesized via low-temperature Na+-Ag+ ion exchange. The spectral features of the nanostructures in the silicate glass matrix as well as their photocatalytic performance were studied in detail. Glass-ceramics containing hybrid metal-semiconductor nanostructures were shown to possess one order of magnitude higher photocatalytic activity compared to their counterparts with metallic and semiconductor nanostructures. Hybrid metal-semiconductor nanostructures allow enhancement of the net density of photogenerated hot electrons.