The molecular structure of trans-bis(pyridin-3-yl)ethylene (3,3′-bpe), C₁₂H₁₀N₂, as determined by single-crystal X-ray diffraction is reported. The molecule self-assembles into two dimensional arrays by a combination of C—H...N hydrogen bonds and edge-to-face C—H...π interactions that stack in a herringbone arrangement perpendicular to the crystallographic c-axis. The supramolecular forces that direct the packing of 3,3′-bpe as well as its packing assembly within the crystal are also compared to those observed within the structures of the other symmetrical isomers trans-1,2-bis(n-pyridyl)ethylene ( n , n ′-bpe, where n = n′ = 2 or 4).