A key parameter in the performance of organic electronics devices is the mobility of charges. On the macroscopic level, it has been demonstrated that the highest charge carrier mobilities are obtained in highly ordered single-crystalline materials.[1] However, the inherent fragility of single crystals poses serious technological problems, thus considerably limiting their practical applications. An interesting alternative is offered by discotic mesogens, which are typically composed of a central aromatic core substituted with flexible alkylic chains.[2] Cores tend to form columnar stacks, maximizing porbital overlap between adjacent molecules and thus favoring a one-dimensional migration of charge carriers.[3] Furthermore, the inherent fluidity of liquid crystals induces advantageous properties, such as the ability to self-heal structural defects and easier alignment and processing from the isotropic phase. However, fluidity is also associated with intrastack dynamism of the functional units that reduces carrier mobility in the bulk. Therefore, the preferred strategy for improving mobility in discotic mesophases has been the enhancement of the intermolecular order within the stacks. To achieve this goal, different approaches have been explored: 1) linking the cores to peripheral alkylic chains through bulky moieties; [4] 2) introducing functional groups providing directional interactions [5] (e.g. hydrogen bonds); or even 3) inducing helical columnar arrangements that provide a higher degree of order. [4a, 6, 7] Herein, we present an experimental study on new triindole mesogens, one of them exhibiting very high hole mobility (m % 1.4 cm 2 V À1 s À1 ). We show how carrier mobility in such compounds does not depend only on the degree of intracolumnar order along the columns by itself, but also, as in most p-conjugated organic semiconductors, on the stacking distance between molecules, which usually decreases with increasing order.[8] Moreover, results show how intracolumnar molecular distance can be controlled by a suitable choice of the spacers between the aromatic core and the peripheral chains, underlining the promising role of ethynyl moieties as linkers in high-mobility columnar phases.Heptacyclic 10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (triindole) was recently introduced as a new core for discotic mesogens.[9] Attachment of six decyl chains (compound 1 in Scheme 1) resulted in columnar hexagonal mesophases, although no stacking periodicity was observed. Despite the intracolumnar disorder, 1 has a high hole mobility m = 0.02 cm 2 V À1 s À1 in the mesophase. In an attempt to raise the mobility values by increasing intracolumnar order, we have investigated the effect of sterically demanding phenyl (compound 2) and rigid alkyne (compound 3) spacers between the peripheral alkyl chains and the central triindole core.The synthesis of 2 and 3 is described in the Supporting Information. Both compounds are obtained as crystalline solids. On heating, they show mesomorphic behavior between room temperature and ...