Attempts to prepare SbPh₂F by the modification of methods which give the corresponding chloride have not been successful, but this compound can be obtained by treating SbF₃ with [NH₄]₂[SiPhF₅]. Comparison of the mass spectra of SbPh₂F and SbPh₂Cl suggests the formation of strong fluorine bridges in the former, which has been confirmed by an X-ray analysis. Crystals of SbPh₂F are orthorhombic with a= 8.18(1), b= 11.04(1), c= 12.02(1)Å, space group P2₁2₁2₁, and Z= 4. Atomic positions have been determined by Patterson and Fourier methods from X-ray diffractometer data and refined by least squares to R 0.042 for 1 170 reflections. The structure consists of infinite chains of SbPh₂F units, resulting from the formation of strong intermolecular fluorine bridges [Sb ⋯ F 2.221(5)Å]; the corresponding intramolecular Sb–F distance is 2.166(5)Å and the angle at the bridging fluorine is 140.2(3)°. The antimony lone pair of electrons is stereochemically active giving a structure based on a trigonal bipyramid with fluorines in axial positions and the phenyl groups occupying two of the equatorial positions. The mean Sb–C distance is 2.13 Å and angle between the phenyl groups [C(1)–Sb(1)–C(7)] is 99.9(4)°.