Fluorocarbon nanostructures possess an outer halogenated crown that plays the role of an interface towards their environment and whose properties are then crucial for anticipating the integration of the latter materials in nanotechnology processes. Therefore, the result of fluorine addition to nanocarbon frames has been investigated here with the help of IR and XPS spectroscopies, and the role played by the pristine lattice curvature and the addend's addition scheme on the physicochemical characteristics of this outermost shell is experimentally established. The relevant paradigm of supposedly ionocovalent C-F terminations in these nanomaterials is shown to be obsolete.