Following unsuccessful attempts to confirm the existence of previously reported antimony(I) fluorosulfate, Sb(SO3F), the reaction of antimony and fluorosulfuric acid is reinvestigated and synthetic routes are developed that allow the preparation of polymeric [SbF2(SO3F)](x), [SbF(SO3F)(2)](x), and [Sb(SO3F)(3)](x). Recrystallization from fluorosulfuric acid is found to produce single crystals of all three materials, which are suitable for molecular structure determinations by single-crystal X-ray diffraction. Crystals of [SbF2(SO3F)](x) are orthorhombic, a = 13.4035(6) Angstrom, b = 7.1852(6) Angstrom, c = 5.0239(9) Angstrom, Z = 4, and space group Pna2(1). Crystals of [SbF(SO3F2)](x) are monoclinic, a = 10.7302(8) Angstrom, b = 4.899(1) Angstrom, c = 13.671(1) Angstrom, b = 111.253(7)degrees, Z = 4, space group P2(1)/c. Crystals of [Sb(SO3F)(3)](x) are hexagonal, a = 9.5718(9) Angstrom, c = 17.283(1) Angstrom, Z = 6, and space group P6(5). Data for all three compounds were collected to high resolution (Mo radiation, 2 theta(max) = 100 degrees) in order to provide accurate structural information.