Four tetracatenar (L1–L4) and one hexacatenar (L5) ligands, derived from the diaza-18-crown-6 framework, are synthesized and characterized. In these ligands, the amine functions are fitted with benzoyloxybenzyl linker groups, attached either with a carbonyl function (L1) or a methylene bridge (L2–L5) and bearing alkoxy chains, R, of various lengths: R = OCH3 for L2, OC10H21 for L3 and L5, OC12H25 for L1, and OC16H33 for L4. The non-mesomorphic ligands L1 and L3–L5 react with various lanthanide salts to give complexes forming thermotropic hexagonal columnar phases, as ascertained by thermal, optical and small-angle X-ray diffraction methods. The length of the alkoxy chains (L3 and L4) does not much influence the mesogenic behaviour, irrespective of the linker function, the number of alkoxy chains, the counterion or the lanthanide ion. The best systems proved to be the nitrato lanthanide complexes with L3, which present a Colh phase over 100 °C (up to 147 °C for La) with melting transition temperatures between 58 (La) and 86 (Tb) °C. In the case of [Eu(NO3)3L3], chosen as a representative example of all the complexes in this analysis, the inter-column separation of 29.2 Å agrees well with the packing of cylindrical columns resulting from an alternated stacking of the molecules, in which the two mesogenic arms extend on the same side, i.e. stacking the molecules in a bent conformation. The liquid crystalline phases containing Eu and Tb display metal-centred emission, meaning that these complexes are interesting building blocks for the design of luminescent liquid crystalline materials.