Specially fluorinated polycyclic aromatic hydrocarbons (F-PAHs) are of interest as precursors for transition metal catalyzed CVD growth of chiral-index pure single-walled carbon nanotubes as well as for the rational synthesis of fullerenes. Laser desorption/ionization of a prototypical F-PAH has recently been shown to lead to C60 via a sequence of regioselective intramolecular cyclodehydrofluorination steps: C60H21F9 → C60H20F8 + HF → C60H19F7 + HF ... → C60 (Kabdulov et al. Chem.–Eur. J. 2013, 19, 17262). We have studied the thermal stability of solid C60H21F9 films on graphite under UHV conditions toward exploring the extent to which such intramolecular dehydrofluorination can also occur on a hot chemically inert surface and to what extent intermolecular interactions influence such transformation processes. C60H21F9 films were probed in situ by ultraviolet photoionization, X-ray ionization, Raman spectroscopy, and thermal desorption mass spectrometry, as well as by ex situ atomic force microscopy. Heating multilayer films results first in C60H21F9 emission from the bulk (peaked at ∼630 K) followed at higher temperatures by desorption from the interface region (in the range 750–850 K). Sublimation from the interface region is also associated with some on-surface cyclo-dehydrofluorination as indicated by C60H21–nF9–n, n = 1, 2, 3 emission. C60 was not observed in the desorbed material suggesting that complete cage closure cannot be achieved on HOPG. Furthermore, C60H21F9 deposits cannot be fully removed from HOPG. Instead, competing on-surface polycondensation of reactive intermediates yields a fluorinated carbon phase, which remains stable up to at least ∼1000 K. To complement these studies we have also used mass selective ion beam soft-landing to probe the desorption properties of monodispersed films consisting of mass-selected C60H21–nF9–n fragments, n = 1, 2.