A novel organically templated layered cerium phosphate fluoride [(CH)(2)(NH3)(2)](0.5)[(CeF3)-F-IV(HPO4)] has been synthesized by hydrothermal synthesis technology, and characterized by means of single-crystal X-ray diffraction. Its unique layered structure is based on a network of novel CeO3F5 polyhedral and PO4 tetrahedral. The [NH3(CH2)(2)NH3](+) cations contact with the adjacent layers via hydrogen bonds to compensate the negative charge of the inorganic framework.