The introduction of gallium and germanium into the sodalite framework has been achieved by hydrothermal and low temperature solution routes for a wide range of anions. This yields materials of general composition Na8[ABO4]6·X2, where A=Al and Ga, B=Si and Ge, and X includes Cl−, Br−, I−, (ClO3)−, (BrO3)−, (HCOO)−, (MnO4)−, (SCN)− and (SeCN)−. Lithium and potassium exchanged derivatives of certain sodalites have also been prepared via reaction in nitrate melts. Intra-cage reactions performed on selected samples have permitted the preparation of such species as aluminogermanate sulphur and selenium ultramarines. Products have been characterised by powder X-ray and neutron diffraction, infra-red, Raman and magic angle spinning nuclear magnetic resonance spectroscopy, thermogravimetric analysis and flame photometry.