18 new iron fluorophosphates and a chlorofluorophosphate have been synthesised hydrothermally in a fluoride-rich medium, using FeF2, FeF3, Fe, HPF6. HCl, monovalent metal fluorides as reactants and amines as templating agents. Products have been fully structurally characterised using single crystal X-ray diffraction, and the stability of some compounds investigated using thermogravimetric analysis. Reaction in fluoride-rich conditions produce ribbon-like, layer and framework structures containing new and unusual structural motifs based on the linking of Fe(O,F)6, PO3F, and PO2(OH,F)2 polyhedra. Structures exhibiting inter-layer spaces and channels are frequently lined by terminal fluoride anions of the PO3F, PO2(OH,F)2 and Fe(O,F)6 polyhedra.