The crystal structures of α-F 2 and β-F 2 have been reinvestigated using neutron powder diffraction. For the low-temperature phase α-F 2 , which is stable below circa 45.6 K, the monoclinic space group C2/c with lattice parameters a=5.4780(12), b=3.2701(7), c=7.2651(17) Å, β=102.088(18)°, V=127.26(5) Å 3 , mS8, Z=4 at 10 K can now be confirmed. The structure model was significantly improved, allowed for the anisotropic refinement of the F atom, and an F−F bond length of 1.404(12) Å was obtained, which is in excellent agreement with spectroscopic data and high-level quantum chemical predictions. The high-temperature phase β-F 2 , stable between circa 45.6 K and the melting point of 53.53 K, crystallizes in the cubic primitive space group Pm (Formula presented.) n with the lattice parameter a=6.5314(15) Å, V=278.62(11) Å 3 , cP16, Z=8, at 48 K. β-F 2 is isotypic to γ-O 2 and δ-N 2 . The centres of gravity of the F 2 molecules are arranged like the atoms in the Cr 3 Si structure type.