In the past five years we introduced a novel approach to the synthesis and isolation of various classes of polyperfluoroalkylated PAHs and polyheterocyclic compounds. This approach is based on the gas-phase high-temperature reactions between parent PAHs and perfluoroalkyl iodides, either in the presence of Cu promoter, or without. In most cases, several most thermodynamically stable isomers with three or more (depending on the size of PAH core) perfluoroalkyl groups were formed by direct hydrogen substitution. For some PAH substrates, alternative synthetic methods were developed permitting access to even larger sets of fluorinated PAH acceptors. This presentation will feature our findings in the molecular structural analysis, crystal packing, general trends of electronic and photophysical properties in solution and in the gas phase, and will discuss the applicability of the new materials in specific optoelectronic devices.