Superionic PbSnF4 can be prepared using a variety of different methods. It crystallizes in various different unit-cells. All structures are closely related to that of the fluorite type structure, with various degrees of order/disorder and different types of superstructures. Reaction of lead(ll) nitrate and stannous fluoride in water gives highly stressed and highly oriented tetragonal α-PbSnF4, however, in HF/H2O, it gives orthorhombic O-PbSnF4, which is also stressed but less. Reactions of solid α-PbF2 with an aqueous solution of SnF2, in excess SnF2, also gives stressed α-PbSnF4. Solid state reactions of SnF2 and PbF2 give unstressed and much less oriented α-PbSnF4 at 250°C, whereas tetragonal β-PbSnF4 is obtained above 270°C and is quenchable to ambient temperature. At 390°C, cubicy-PbSnF4 is obtained, however, this is not quenchable. Ball milling of o-PbSnF4 gives stressed α-PbSnF4, and ball milling of a- and β-PbSnF4 gives microcrystalline γ-PbSnF4. Annealing the latter gives unstressed and non oriented α-PbSnF4. Stirring a slurry of microcrystalline γ-PbSnF4 in water gives α-PbSnF4 except the one originating from o-PbSnF4, which gives back o-PbSnF4. The texture of these phases, and therefore the macroscopic properties related to it, can be drastically modified by modifying the method of preparation.