AbstractIsothiocyanates having the NCS‐group bound directly to the CC‐bond — the vinyl isothiocyanates — are of high synthetic interest because this type of heterodienes is a suitable precursor for heterocyclic compounds and derivatives of thiocarbamic acid. They cannot be prepared by standard methods.In this review we report 1) the synthesis of vinyl isothiocyanates by the reaction of nitrogen compounds with thiophosgene and other sulphur compounds, SNV‐reactions, elimination of HX, addition of HSCN to alkynes, cleavage of heterocycles and by miscellaneous methods 2) structure and reactivity of the vinyl isothiocyanates and 3) the reactions of these conjugated mustard oils with numerous nucleophiles and their behaviour as heterocumulenes in cycloadditio