The disulfide dication salt, 1,5-dithioniabicyclo[3.3.0]octane bis(trifluoromethanesulfonate) (3), was isolated from the reaction of 1,5-dithiacyclooctane 1-oxide with trifluoromethanesulfonic anhydride. Two-electron oxidation of 1,5-diselenacyclooctane with two equivalents of NOPF6 or NOBF4 gave the first diselenide dication salt, 1,5-diselenoniabicyclo-[3.3.0]octane bis(hexafluorophosphate) or b