Nine new manganese(III) fluorophosphates have been synthesised hydrothermally in a fluoride-rich medium, through the use of MnF3, 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 Mn(O6−n,Fn) octahedra, with n averaging 2.8 over the family of compounds. The Mn(III), d4, oxidation state is stabilised under these reaction conditions and products frequently show Jahn–Teller distorted Mn(O,F)6 units with axially elongated Mn–O or, less commonly, Mn–F distances. Structures exhibiting inter-layer spaces and channels frequently have these lined by terminal fluoride anions of the PO3F, PO2(OH,F)2 and Mn(O,F)6 octahedra.