A new fluoroaluminophosphate chain, denoted AlPO-CJ10, has been synthesized in the system Al(PrO i ) 3 –H 3 PO 4 –hexamethyleneimine–HF–TEG and its structure solved by single-crystal X-ray diffraction analysis. It is characterized by X-ray powder diffraction (XRD), ion-selective electrodes (ISE), inductively coupled plasma (ICP), thermogravimetric (TG), and elemental analyses. The compound has an empirical formula of [AlP 2 O 5 (OH) 3 F]·[C 6 H 12 NH 2 ] and crystallizes in the orthorhombic space group Pnma (No. 62) with a=25.547(10) Å, b=6.915(2) Å, c=7.179(2) Å, Z=4, R 1 =0.0550, and wR 2 = 0.1382. Its structure is built up by alternation of tetrahedral PO 3 (OH) and PO 2 (OH) 2 units and octahedral AlO 4 F 2 units to form one-dimensional AlP 2 O 8 H 3 F − macroanionic chains containing an infinite –Al–F–Al– linkage. The inorganic chains are held together by protonated hexamethyleneimine through H bonds.