This work presents a Raman based approach for the rapid identification of the molecular conformation in a series of new 2,3-thienoimide capped quaterthiophenes, whose crystal structures were determined by synchrotron radiation X-ray powder diffraction. These systems display two conformational polymorphs, known as forms A and B, as a result of the anti–anti–anti and syn–anti–syn arrangements of the quaterthiophene cores. In a micro-Raman and computational study, the spectroscopic differences between the conformers were detected and proved to be suitable markers for polymorph identification. Thus, the synergic employment of diffraction and Raman spectroscopy techniques yields a full and reliable characterization of 2,3-thienoimide capped quaterthiophene compounds in their solid state.