Chemosynthetic aluminosilicate inorganic polymers exhibiting photoluminescent properties were prepared by introducing rare earth activator ions (Sm3+ or Eu3+) into the aluminosilicate structure by ion exchange. Under similar to 400 nm excitation, the materials showed the characteristic 4f-4f emission peaks of Sm3+ and Eu3+ ions and also broad emission bands in the blue and green regions that were also exhibited by the unexchanged inorganic polymer host. The host and the corresponding phosphors were characterised by XRD, Al-27 and Si-29 MAS NMR, PIXE and XPS. The photoluminescence intensities of the aluminosilicate inorganic polymers containing Sm3+ and Eu3+ were considerably enhanced by heating in air at > 800 degrees C. The best phosphors were heated at 1200 degrees C, forming a mixture of crystalline KAlSi2O6 (leucite) and the residual aluminosilicate inorganic polymer.