<p>On treatment with a cationic Pd(II) catalyst in the presence of BF₃·OEt₂, 1,1-difluoroalkenes and 1,1,2-trifluoroalkenes underwent Friedel-Crafts-type ring closures (direct activation) to afford pinpoint-monofluorinated and pinpoint-vic-difluorinated phenacenes (F-phenacenes), respectively. Treatment of 1,1-difluoroallenes with an InBr₃ catalyst facilitated domino cyclization (indirect activation) leading to the synthesis of F-phenacenes and related F-PAHs. Using the formed F-PAH library, the physical properties of these compounds were investigated. Notably, the HOMO-LUMO energy gaps of F-picenes, consisting of five benzene rings, were smaller than that of the corresponding fluorine-free picene by 0.02-0.26 eV. The HOMO energy levels of F-picenes were lowered by 0.10-0.22 eV, leading to enhanced resistance of these materials to aerial oxidation. 5-Fluoropicene and 13-fluoropicene exhibited p-type semiconducting behavior [5-fluoropicene: 2.8×10⁻⁵ cm²/Vs (vacuum deposition); 13-fluoropicene: 6.6×10⁻² cm²/Vs(vacuum deposition), 1.3×10⁻⁴ cm²/Vs (spin casting)].