Eleven new copper fluorophosphate frameworks have been synthesised hydrothermally in a fluoride-rich medium, through the use of CuF2 HPF6 and monovalent metal fluorides as reactants. Products have been structurally characterised using single crystal X-ray diffraction. Reaction in fluoride-rich conditions produces chain, layer and three dimensional framework structures containing new and unusual structural features based on the linking of PO3F, PO2(OH,F)2 and Cu(O,F)n polyhedra (n = 4–6). Analysis of these structures, in terms of the copper coordination environments and their linkage dimensionalities, shows that these features are dependent on fluoride-content of the reaction medium and, therefore, the level of fluoride ion incorporation into the product materials. Structures exhibiting inter-layer spaces and channels frequently have these lined by terminal fluoride anions of the PO3F, PO2(OH,F)2 and Cu(O,F)n polyhedra.