Here we present some of the last results in studying the ability of halo-derivatives of perfluoroalkanes and arenes, behaving as electron-acceptor modules, to give rise to supramolecular assembly through halogen bond to neutral or charged electron-donors. The strength of the halogen bond is there enforced by the presence of the fluorine atoms, so that it is quite easy to produce linear assembly of dimers AB, trimers BAB, or non-covalent polymers ...ABAB..., where A is a mono- or dihaloperfluoro-alkane/arene, acting as acid, and B is such a base as I-, Br-, the nitrogen atoms of amines and pyridines or the oxygen atom of pyridine-N-oxides. Dimers, trimers or polymers are obviously formed according to the numbers of interacting sites in A and B.