The imidazole disulfide and diselenide dicataions were conveniently isolated for the first time by treating imidazole thione or imidazole selone with bismuth(III) triflate or copper perchlorate hexa-hydrate in very good yield. These new salts were characterized by elemental analysis, FT-IR, solid state UV-vis, thermogravimetric analysis and single crystal X-ray diffraction techniques. Interesting thermal properties and unusual bonding situations were observed for these dichalcogenide salts. ©2015 Elsevier B.V. All rights reserved.