A theoretical investigation on the interaction of various sulfides and their fluorinated counterparts (H2S, HSF, F2S, CH3SH, CH3SF CH2FSH, CH2FSF, NH2SH, NH2SF) with atomic chlorine has been carried out using density functional theory (DFT) based LC-BLYP/aug-cc-pVTZ and sophisticated ab initio CCSD(T)/aug-pVQZ methods. The present study is intended to discuss the influence of the substituents implanted at the sulfur atom on the bonding parameters. The optimized geometries revels that intermolecular S center dot center dot center dot Cl distances are short and range between 2.423 and 2.561 angstrom. A strong contraction of the S-F bond is also predicted. Two-center-three-electron S center dot center dot center dot Cl bonds are formed; the interaction energies are large and range form -33.9 to -70.1 kJ mol(-1 ).Very surprisingly, the interaction energies are greater and the intermolecular distances are shorter for F-substituted sulfides than for unsubstituted ones. This is in complete contrast with the lower proton affinities and less negative electrostatic potentials of fluorinated sulfides. AIM analysis, the charge transfer from the sulfur atom to the Cl atom, and the spin densities on the Cl and S atoms are considered to explain this unusual behavior. The hyperconjugation energies from the LP(F) to the sigma*(S-Cl) antibonding orbital can be considered as one of the stabilizing factors for the greater stability of the fluorinated complexes over the nonfluorinated ones.