Thiophenes are an important class of molecules in fields as diverse as petrochemistry, molecular electronics, and optoelectronics. Thiophenic submolecular motifs are thought to play a role in molecular association and nanoaggregation phenomena in both pure materials and natural and synthetic mixtures. Vibrational (infrared and Raman) spectroscopy provides the means to characterize these species. In this work far-infrared photoacoustic and low-frequency Raman spectra of a series of polycyclic aromatic hydrocarbons containing sulfur have been measured and interpreted using DFT calculations based on a perturbational-variational method coupled with potential truncation. The approach and outcomes illustrate how inter- and intramolecular vibrations for thiophenic systems in single and multicomponent mixtures can be discriminated. This work offers the perspective to search the inter- and intramolecular signatures of the main submolecular motifs and heteroelements postulated as being present in the asphaltenes.