A low-temperature polymorph of 1,1′:3′,1′′:3′′,1′′′:3′′′,1′′′′-quinquephenyl (m-quinquephenyl), C₃₀H₂₂, crystallizes in the space groupP2₁/cwith two molecules in the asymmetric unit. The crystal is a three-component nonmerohedral twin. A previously reported room-temperature polymorph [Rabideau, Sygula, Dhar & Fronczek (1993).Chem. Commun.pp. 1795–1797] also crystallizes with two molecules in the asymmetric unit in the space groupP\overline{1}. The unit-cell volume for the low-temperature polymorph is 4120.5 (4) ų, almost twice that of the room-temperature polymorph which is 2102.3 (6) ų. The molecules in both structures adopt a U-shaped conformation with similar geometric parameters. The structural packing is similar in both compounds, with the molecules lying in layers which stack perpendicular to the longest unit-cell axis. The molecules pack alternately in the layers and in the stacked columns. In both polymorphs, the only interactions between the molecules which can stabilize the packing are very weak C—H...π interactions.