The simplest alkynyl thiocyanate HCCSCN has been synthesized and characterized for the first time. HCCSCN is surprisingly stable at room temperature but undergoes photoisomerization in an Ar-matrix (10 K) to yield the novel sulfenyl isocyanide HCCSNC and thioketene NCC(H)CS. The isomeric isothiocyanate HCCNCS, missing in the photochemistry of HCCSCN, can be generated through the photodecarbonylation of propiolyl isothiocyanate.