A salt-inclusion stannosilicate, [Na3F][SnSi3O9], has been synthesized using a flux-growth method and characterized by single-crystal X-ray diffraction. The structure consists of six-membered silicate rings linked via corner sharing by SnIVO6 octahedra to form a 3-D framework that delimits two types of channels. The F atoms and Na atoms are located in the structural channels and form a dimer with the anti-Al2Cl6(g) structure. This stannosilicate adopts a new structure and is the first metal silicate that contains both Na+ and F- ions in the channels. The 19F and 29Si MAS NMR and 23Na MQMAS NMR spectra are consistent with the crystallographic results.