Molecular interaction of perfluoroalkyl (Rf) compounds has long been discussed on an extended theory of normal alkyl compounds. When Rf-specific bulk properties depending on the molecular packing structure are taken into account, however, the conventional polarizability theory has a big inconsistency especially with the high melting point. Here, we present a new viewpoint to totally uniform the conventional theories for systematically accounting for the bulk properties of Rf compounds. With the organized theoretical framework, the conventional understanding based on polarizability proves to be partly true, but it misses the molecular orientation effect, which is specifically necessary for the Rf compounds. (C) 2015 Elsevier B.V. All rights reserved.