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We report the formation of easily accessible hydrogen‐bonded columnar discotic liquid crystals (LCs) based on tris‐benzoimidazolyl benzene ( TBIB ) and commercially available fatty acids. By increasing the length of the fatty acid, the temperature range of liquid crystallinity was tuned. Introducing double bonds in octadecanoic acid lowered the crystallization temperature and increased the temperature range of the mesophase. Surprisingly, dimerized linoleic acid also forms an LC phase. When using branched aliphatic acids with the branching point close to the acid moiety, the mesophase was lost, whereas phosphonic acid or benzenesulfonic acid derivatives did have a mesophase, showing that the generality of this approach extends beyond carboxylic acids as the hydrogen‐bond donor. Furthermore, a polymerizable LC phase was obtained from mixtures of  TBIB  with a methacrylate‐bearing fatty acid, providing an approach for the fabrication of nanoporous polymer films if the methacrylate groups are polymerized. Finally, the higher solubility of methyl‐ TBIB  was used to suppress phase separation in stoichiometric mixtures of the template molecule with fatty acids.

Easily Accessible Thermotropic Hydrogen‐Bonded Columnar Discotic Liquid Crystals from Fatty Acid– Tris‐Benzoimidazolyl Benzene Complexes