Intermolecular interaction in pure dimethyl sulfoxide DMSO solvent are investigated using combined approach to relate IR and Raman spectral manifestations of formation of different associates with numerical results. It is established that the stable chain and cyclic dimmers are formed due to the interaction of parallel and antiparallel oriented molecular dipoles and hydrogen bonding between the oxygen atom of the S=0 group of one DMSO molecule and the hydrogen atom of the CH group of other DMSO molecule.