The existence of a second polymorphic form of the hole transport material N,N′-diphenyl-N,N′-bis(3,3′-methylphenyl)-[(1, 1′-biphenyl)]-4,4′-diamine has been confirmed using both Pawley and Rietveld refinement of structural information against high-resolution synchrotron X-ray powder diffraction data. © The Royal Society of Chemistry 2005.