The molecular design of a series of perfluoroarylbisselanes (30–68 %) o-, m- and p-(ArFSe)2C6F4 and (ArFSe)2C12F8 (ArF=C6F5 and p-C6F4CF3) were achieved through the reaction of ArFSeCu with diiodoperfluoroarenes bearing phenyl and biphenyl rings. Analysis of the X-ray diffraction (XRD) data for the resulting perfluoroaromatic bisselanes 5–12 demonstrated their significant potential for constructing supramolecular architectures through tandem noncovalent interactions, including chalcogen bonding (ChB) and πhole−π interactions. 1,2-Bis(pentafluorophenylseleno)tetrafluorobenzene 5 was cocrystallized with dibenzyl ether, yielding the adduct 52⋅Bn2O, which exhibited a triad structural motif. Its XRD data provided structural insights into the ChB-based catalysis mechanism of Friedel-Crafts type reaction involving benzyl ether derivatives. Comprehensive density functional theory studies: energy decomposition analysis (EDA), molecular electrostatic potential (MEP) assessments, van der Waals potential evaluations, electrostatic potential and energy density (ED/ESP) plots, as well as natural bond orbital (NBO) analysis – revealed that Se⋅⋅⋅O chalcogen bonding (10.1 kcal/mol) and πhole−π interactions (12.6 kcal/mol) contribute comparably to the overall energetics, thus playing a significant role in guiding molecular assembly.