Ethyl 2-(methylthiomethyl)phenyl selenide 1a, telluride 1b and ethyl 2-(methylselanylmethyl)phenyl telluride 1c were prepared and treated with 1 equivalent of triflic anhydride (Tf2O) or 2 equivalents of nitrosonium salts (NOBF4 or NOPF6) at low temperature to generate the corresponding selenathia, tellurathia and telluraselena dications(2a, 2b and 2c), the structures of which were determined by NMR spectroscopy and 2b was successfully isolated.