We disclose here the invention of a new class of extensively fluorinated porous materials which can bind aliphatic and aromatic hydrocarbons, fluorocarbons, and Freons with high weight adsorption capacities. These molecular materials are constructed from a central core (which can have linear, trigonal, tetragonal or hexagonal geometry) and 2-6 radially projecting arms which bear fluorinated and electron-rich groups in an alternating arrangement. Pi-pi stacking between electronrich and electron-poor nuclei in these arms creates the porous structure. These materials can bind many fluorophilic and nonpolar guests. Significantly, they bind ortho- and meta-xylenes well (20 weight % and more), while they essentially do not bind para-xylene {<1 weight %). This feature could be useful in the separations of these three species, which is of immense relevance in chemical and petrochemical industries.