Abstract4-(Dimethylamino)thiopivalophenone was prepared from 4-bromo-N,N-dimethylaniline, pivalonitrile and carbon disulfide. Its crystal and molecular structure was determined by single-crystal X-ray diffraction. The experimentally determined bond distances, bond angles and torsion angles are indicative of a significant contribution of a dipolar (“quinodimethane”) resonance structure to the electron distribution in the molecule. Quantum chemical calculations corroborate these results. The calculations, furthermore, provide an explanation of the arrangement of the molecules in the crystal.