The promesogenic hexacatenar tridentate ligands L3(Cn) (I shape) and L4(Cn) (V shape) react with trivalent lanthanide trifluoroacetates, Ln((CF3CO2)3, to give either monometallic [Ln(Li(Cn))(CF3CO2)3] or trifluoroacetato-bridged bimetallic [Ln(Li(Cn))(CF3CO2)3]2 complexes in the solid state, as exemplified by the crystal structures of [Lu(L4(CO))(CF3CO2)3(H2O)], [Lu(L4(CO))(CF3CO2)3]2, and [La(L3(C4))(CF3CO2)3]2. Although the dimerization process is influenced by the competiting complexation of anions or solvent molecules, the coordination of CF3CO2- instead of NO3- to Ln(III) produces a significant lengthening of the Ln-N(ligand) bond distances. This translates into a considerable decrease of the affinity of the Li(C12) (i = 3, 4) ligands for Ln(CF3CO2)3 in solution, thus leading to significant dissociation of the [Ln(Li(C12))(CF3CO2)3] complexes at millimolar concentrations. The thermal properties of these complexes also suffer from their limited thermodynamic stability, and the thermotropic liquid crystalline phases produced at high temperatures reflect mixtures of different species. However, a hexagonal columnar organization characterizes the main component in the mesophases obtained with [Ln(L3(C12))(CF3CO2)3] at high temperature. A tentative interpretation of the small-angle X-ray scattering (SAXS) profiles suggests that disklike dimers of [Ln(L3(C12))(CF3CO2)3]2 are packed along the columnar axes. For [Ln(L4(C12))(CF3CO2)3], SAXS profiles are compatible with a lamellar organization in the mesophases originating from the existence of rodlike dimers of [Ln(L4(C12))(CF3CO2)3]2 as the major component in the liquid-crystal state.