(NH4)(0.16)K-1.84[Ti2F2(PO4)(2)(PO3OH)] (1) has been synthesized under hydrothermal conditions. The structure, the composition, and the thermal stability of 1 were determined by single-crystal X-ray diffraction; inductively coupled plasma-optical emission spectroscopy; IR spectroscopy; elemental analysis; thermogravimetric analysis-differential scanning calorimetry-mass spectrometry; and solid-state H-1, P-31, and F-19 NMR, and the phase purity of the bulk sample was checked by powder X-ray diffraction. Complex 1 is a fluorotitanophosphate having a unique lamella framework with both TiO5F octahedra and PO3OH tetrahedra on the surface of the layer, which leads to two different hydrogen bondings involving both P-OH and Ti-F groups.