A lightweight organic material, trans-4′-dimethylamino-4-nitro-α-cyanostilbene, exhibits notable charge carrier mobility (∼10 -4 cm 2 V -1 s -1 ). The non-centrosymmetric material also displays moderate second harmonic generation activity. This is one of the rarest examples of small organic materials displaying semiconductor characteristics. The charge-transfer pathway as elucidated via high-resolution single-crystal X-ray diffraction data based "energy frameworks" and "experimental charge density" analyses is assessed by measuring the charge carrier mobility using the space charge limited current technique on pure single-crystal diode devices. These advanced structural analyses clearly demonstrate that charge transport in organic crystals is purely governed by its molecular packing, especially the π-π stacking geometry. The balanced ambipolar charge transport behavior makes this highly soluble and thermally stable organic crystal promising for applications in optoelectronic devices. Moreover, this report introduces the crucial role of energy frameworks and charge density analyses for fundamental understanding of the structure-property relationship in organic semiconductors. Copyright © 2019 American Chemical Society.