Abstract 1,4‴-Dimethoxy-4,1′:4′,1″:4″,1‴-quaterphenylene crystallizes in space group Pbca with a = 7.4989(5) Å, b = 6.1544(3) Å, c = 40.359(2) Å, V = 1862.6(2) Å 3, and Z = 4. In the crystal structure the molecules are arranged in layers, which are stacked in the direction of the crystallographic c-axis. The torsion between the molecules in a layer amounts to 69.06° resulting in a herringbone structure. The phenyl rings of the molecule are approximately planar with a torsion angle of 4.64° between the outer and the center rings. UV/Vis transmission measurements of the colorless crystal reveal a band gap of ~ 3.2 eV.