Octafluoro-1,2-dimethylenecyclobutane, mp. 238 K, was crystallized in situ on a SMART 1000-CCD diffractometer, and high order X-ray diffraction data were collected at 100 K for a charge density determination. A topological analysis was applied and a partitioning of the molecule into atomic regions making use of Bader's zero flux surfaces yielded atomic volumes and charges. Corresponding atomic properties were also derived theoretically from B3LYP/6-311++G(3df,3pd) wavefunctions. While for carbon the volumes and charges are largely dependent on their bonding environment, fluorine has an almost constant atomic volume around 16-17 A3 and a charge between -0.6 and -0.7e, not only in the title compound, but also in two further perfluorinated hydrocarbons, of which the charge densities were determined earlier.