Improved long-range ordering in the columnar mesophase of hexa(para-n-dodecylphenyl)hexabenzocoronene 1 has been achieved by inserting phenyl rings between the extended aromatic core of hexabenzocoronene and the alkyl side chains, which are needed to form liquid crystalline phases. The long-range hexagonal order of the columns is demonstrated by X-ray scattering, while the improved packing of the aromatic cores within the columns and the molecular mobility is probed by a newly developed heteronuclear multiple-quantum MAS NMR technique.