The triphenyltin chloride (TPhTCl) molecular structure was investigated by Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS) and the density functional theory (DFT) modeling. Several conformers with different ordering of the benzene rings were determined in the gas phase and in the dimethyl sulfoxide (DMSO) medium. It was shown that the dihedral angles describing such ordering can change under room conditions. Charge distribution of conformers was analyzed with the use of electrostatic potential (ESP) maps. The formation of weak hydrogen bonds and the rearrangement of the benzene rings to form a complex with negatively charged parts of other molecules were proven by ESP maps. Basing on the results of ESP map analysis, it can be assumed that interaction of TPhTCl molecule with metal cluster results in orientation ordering of the benzene rings. This conclusion was confirmed by modeling the atomistic and electronic structure of TPhTCl molecule adsorbed by the Au₈ cluster, as well as by observing the intense SERS peaks assigned to vibrations of the benzene rings of TPhTCl molecule adsorbed on the surface of the gold inverse opals.