High-temperature phase transition of synthetic kogarkoite, Na3SO4F, has been studied by high-temperature X-ray powder and single-crystal diffraction. The temperature of the phase transition can be estimated as 112.5±12.5 °C. The low-temperature phase, α-Na3SO4F, at 293 K, is monoclinic, P21/m, a=18.065(3), b=6.958(1), c=11.446(1) Å, β=107.711(1)°, Z=12. The structure contains thirteen symmetrically independent Na sites with coordination numbers varying from 6 to 8, and six independent S sites. The high-temperature β-phase at 423 K is rhombohedral, R-3m, a=6.94(1), c=24.58(4) Å, Z=9. The crystal structure of both polymorphs of Na3SO4F can be described as a 9R antiperovskite polytype based upon triplets of face-sharing [FNa6] octahedra linked into a three-dimensional framework by sharing corners. In the α-modification, the SO4 tetrahedra are completely ordered and located