The syn and anti conformers of the hitherto unknown fluorocarbonylsulphenyl fluoride FC(O)SF were formed through the photochemical reactions between OCS and F-2, isolated in solid Ar. The reactions were followed by Fourier transform infrared (FTIR) spectroscopy, and the unknown products were proposed by comparison of the observed IR absorptions with their computed IR spectra. The reactions occur through a 1:1 molecular complex between OCS and F-2, forming the anti-FC(O)SF first, which subsequently transforms into the syn form, through a randomization process. At longer times of irradiation, FC(O)SF decomposes by extrusion of a CO molecule with the concomitant formation of SF2 and the formation of a difluorophosgene molecule, O=CF2. The migration of fluorine atoms in the matrixes is proposed to explain the formation of SF4 and SF6.