The molecular design of crowded hexasubstituted star mesogens based on a benzene core and alternating substitution with oligo(phenylenevinylene) arms and aryl units generates free space between the conjugated arm scaffolds. Various arylcarboxy building blocks, decorated with alkoxy chains have been incorporated in the void by mixing, hydrogen bonding or covalent bonds to the aryl groups. The mesogens assemble in columnar stacks ranging from soft crystals to rectangular and hexagonal columnar liquid crystals, revealed by polarized optical microscopy, differential scanning calorimetry, X-ray scattering and modelling. The stability of the mesophases is crucially influenced by the binding mode of the arylcarboxy guest building blocks. The origin of the variation in clearing temperature is unravelled by modelling, cohesive energy density considerations and solid-state NMR spectroscopy. The control over the transition temperature is important for the fo.