The reaction of the dicarbon Molecule C-2(X(1)Sigma(g)(+)) with hydrogen sulfide, H2S(X(1)A(1)), was investigated under single collision conditions in a crossed beam setup with mass spectrometric detection at an averaged collision energy of 46.0 kJ mol(-1). The experiment was supplemented by electronic structure calculations. The reaction dynamics are dictated by a barrierless addition of dicarbon to the sulfur atom to form a bound H2SCC intermediate followed by two successive hydrogen migrations on the singlet surface to give a singlet thiohydroxyacetylene (HCCSH) species. The latter emits atomic hydrogen to yield the HCCS (X(2)Pi(Omega)) isomer. Possible alternative pathways, the elimination of atomic and molecular hydrogen from a thioketene (H2CCS) intermediate, to synthesize HCCS and CCS are also discussed.