The introduction of silver into the Sm3+-doped sodium–aluminosilicate glasses prepared by Ag+-Na+ ion exchange leads to the formation of different ionic silver species. Under 270 nm/250 nm excitation, effective enhancement of Sm3+ luminescence is ascribed to radiative energy transfer from isolated Ag+ to Sm3+. Under 355 nm excitation, white light emission was realized by combining red orange light emission of Sm3+ with green light emission of Ag+-Ag+ and blue light emission of (Ag2)+. Silver nanoparticles formed by further heat treatment are effective quenchers of luminescence from the corresponding excited states of Sm3+ ions.