New 4,4’-bis(N-vinyl-imidazole-selone)-1,1’-biphenyl was derived from 4,4’-bis(N-vinyl-imidazolium chloride)-1,1’-biphenyl or 4,4’-bis(N-vinyl-imidazolium tetrafluoroborate)-1,1’-biphenyl or 4,4’-bis(N-vinyl-imidazolium hexafluorophosphate)-1,1’-biphenyl in good yield. Subsequently, the bis{4,4’-bis(N-vinyl-imidazole-selenide)-1,1’-biphenyl} tetra tetrafluoroborate was isolated from 4,4’-bis(N-vinyl-imidazole-selone)-1,1’-biphenyl using copper(II) tetrafluoroborate hexahydrate as an oxidizing agent. These new compounds were characterized by elemental analysis, FT-IR, multinuclear NMR and UV-vis studies. In addition, 4,4’-bis(N-vinyl-imidazolium chloride)-1,1’-biphenyl, 4,4’-bis(N-vinyl-imidazolium tetrafluoroborate)-1,1’-biphenyl and [bis{4,4’-bis(N-vinyl-imidazole-selenide)-1,1’-biphenyl} tetra tetrafluoroborate] were characterized by single crystal X-ray diffraction technique. The tetra cationic selenide salt represents the first structurally characterized 32 membered diselenide containing macrocyclic ring. The charge of tetra cationic selenide salt is balanced by four BF4 - ions. The macrocyclic ring is in chair configuration. In solid packing, tetra cationic selenide salt shows an extensive C−H⋅⋅⋅F hydrogen bonding interactions between C-H and BF4 - moieties. Besides, the thermal stability of diselenide containing macrocyclic ring was compared with bis imidazole selone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim