Superbase-promoted chalcogenation of diverse electrophilic reagents with the chalcogens or their anions in multiphase superbase systems became possible owing to the fact that under the action of a very strong hard base such as the “naked” hydroxide ion the elemental chalcogens produce softer and more nucleophilic species which successfully compete for the electrophiles. This explains the paradox that electrophiles such as acetylene, vinylacetylene, phenylacetylene, diacetylene and organo halides, in the presence of strong bases prefer to react with the chalcogens or their anions rather than with the activated hydroxide ion. Ignorance of this fundamental fact for a long time hindered progress in the application of chalcogens for the direct synthesis of their organic derivatives.