Abstract: The reaction of elemental fluorine with structurally unusual hydrocarbon starting materials has been carefully controlled so that structurally analogous perfluorocarbons have been successfully obtained. The syntheses by direct fluorination of perfluoroneopentane, perfluorohexamethylethane, perfluoronorbornane, I-hydroundecafluoronorbornane, perfluorocyclooctane, and monohydropentadecafluorocylcooctane are reported.