The novel microporous germanate (NH4)(4)[(GeO2)(3)(GeO1.5F3)(2)]. 0.67H(2)O was prepared from an aqueous solution containing germanium dioxide, pyridine, hydrofluoric acid, and 2,6-diaminopyridine as a template. The solution was kept at 165 degrees C in a Teflon-lined autoclave for 4 days. Large crystals were produced and studied by X-ray powder diffraction, FTIR, thermal analysis, and elemental analysis. The structure was determined by single-crystal X-ray diffraction. The crystal is orthorhombic, space group Pbcn, with a = 7.0065(4) Angstrom, b = 11.7976(6) Angstrom, c = 19.5200(14) Angstrom, and Z = 4. The structure is a layered framework built up from GeO4 tetrahedral and GeO3F3 octahedral units. The polyhedral units are connected in such a way that they form a zeolite-like porous structure with three- and nine-membered rings. Half of the ammonium ions are located inside the nine-membered rings. The other half are above and below the three-membered rings. The connectivity of the germanium polyhedral units is interrupted along the c axis by ammonium ions and water molecules inserted between the layers.