A high-yield synthesis of the class of (trimethylsilyl)chalcogenolate organic salts [Cat] [TMS-E] (E = S, Se, Te; Cat = BMPyr, DMPyr, NMe4, nBu(3)MeP) is presented. The title compounds have been prepared by the strictly aprotic reaction between the respective bis- se (trimethylsilyl)chalcogenide (TMS,E) and methylcarbonate ionic liquids (ILs). This constitutes a novel reaction behavior of methylcarbonate ILs, acting as a nudeophilic desilylating agent and a Lewis base instead of as a Bronsted base. Thus prepared silylchalcogenolate salts represent an activated form of the multifunctional TMS2E reactant series. Pyrrolidinium TMS-S salts have proven to be excellent precursors for the synthesis of pyrrolidinium hexasulfides. The scope of the desilylation reaction can be extended to other silyl-bearing synthons such as (trimethylsilyl)azide and (trimethylsilyl)cyanide.