A new synthetic approach to highly substituted triphenylboroxines 11 is described. Their mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (SAXS, WAXS). The tris(3,4,5-trialkyloxy)phenyl functionalized derivatives 11b–e showed broad mesophases for a minimum alkyl chain length of C9. The phase widths ranged from 110 K to 77 K near room temperature, thus decreasing with enhanced alkyl chain lengths. Textures observed under POM indicated a columnar hexagonal (Colh) mesophase symmetry that was confirmed by X-ray diffraction experiments.