The photochemistry of FC(O)SSCl isolated in solid Ar was investigated on the basis of the IR spectra of the matrices before and after different times of broad-band UV-visible irradiation. The first process occurring on broad-band UV-visible irradiation was the transformation of the syn-gauche form of FC (O)SSCl into the anti-gauche conformer. FC(O)SCl and ClFC=O were produced, involving the loss of one or two sulfur atoms, respectively. Other mechanisms have originated CO···ClSSF, OCS···ClSF, OCS···ClF, CO···ClSF and CS₂···ClF molecular complexes, identified by the comparison of the experimental IR spectra with that simulated with DFT (B3LYP/6-311+G*) calculations, with the exception of OCS···ClF, which was assigned on the basis of the comparison with reported IR absorptions.