The complexes OCS center dot center dot center dot C6H6, C6H6 center dot center dot center dot Rg, and OCS center dot center dot center dot C6H6 center dot center dot center dot Rg (Rg = He, Ne, Ar, and Kr) have been studied by means of MP2 calculations and QTAIM analyses. The optimized geometries of the title complexes have C-6v symmetry. The intermolecular interactions in the OCS center dot center dot center dot C6H6 center dot center dot center dot Rg complexes are comparatively stronger than that in the OCS center dot center dot center dot C6H6 complex, which prove that the He, Ne, Ar, and Kr atoms have the ability to form weak bonds with the benzene molecule. In QTALM studies, the pi-electron density of benzene was separated from the total electron density. The molecular graphs and topological parameters of the OCS center dot center dot center dot pi C6H6, pi C6H6 center dot center dot center dot Rg, and OCS center dot center dot center dot pi C6H6 center dot center dot center dot Rg complexes indicate that the interactions are mainly attributed to the electron density provided by the it-bonding electrons of benzene and the top regions of the S and Rg atoms. Charge transfer is observed from the benzene molecule to SCO/Rg in the formation of the OCS center dot center dot center dot C6H6, C6H6 center dot center dot center dot Rg, and OCS center dot center dot center dot C6H6 center dot center dot center dot Rg complexes. Molecular electrostatic potential (MEP) analyses suggest that the electrostatic energy plays a pivotal role in these intermolecular interactions.