Two homologues of novel triphenylene mesogens possessing -O(CH2)(3)CF3 (F1) and -O(CH2)(3)(CF2)(5)CF3 (F6) were synthesized and investigated on the mesomorphic behavior to reveal that these show a hexagonal columnar (Col(h)) mesophase. The mesomorphic behavior is obviously different from those of the corresponding hydrocarbon homologues, -O(CH2)(3)CH3 (C1) and -O(CH2)(8)CH3 (C6). Interestingly, it was found that F1 shows a disordered Col(h) phase, though C1 forms only a plastic hexagonal columnar (Col(hp)) mesophase.