Stilbene and its derivatives have a wide application in materials science and biomedical investigations where they are used as the active optical medium or bioactive agents. To provide these researches with new knowledge about stilbenes properties we have performed the structural and spectroscopic analysis of three amino derivatives of trans-stilbene. The DFT calculations in hybrid B3LYP version employing 6-31G (d,p) basis set were used to support the experimental results. The calculated optimized geometries together with the crystal structure obtained from X-ray analysis indicate that all three molecular structures include practically planar stilbene moiety with almost coplanar amino group. The inversion center was revealed in the structure of 4,4′-diaminostilbene. The Raman and IR spectra were registered for solid state in the range of 150–3500 and 500-3500 cm⁻¹, respectively. On the basis of good agreement between the computed frequencies and experimental ones, the thorough vibrational assignment was made. The vibrations of phenyl rings, ethylenic bridge and amino (dimethylamino) group are discussed in detail. The main features of vibrational spectra are revealed for the considered stilbene dyes.