Organic thiocyanates widely exist in natural products, and act as important precursors for organic synthesis. An efficient dithiocyanation of alkynes with N-thiocyanato-dibenzenesulfonimide (NTSI) as the SCN + cation and ammonium thiocyanate as the SCNanion sources has been developed. Highly active electrophilic reagent NTSI could react with various types of alkynes to build C(sp 2 )À SCN bond to provide a variety of dithiocyanato olefin compounds under simple and mild conditions. Trace amount of water is beneficial to the dissociation of ammonium thiocyanate, which makes the SCNanion easier to participate in the reaction. The protocol owns a broad substrates scope including terminal and internal, alkyl and aryl alkynes, excellent functional group tolerance and good regioselectivity.