Two homologues, C6F4 and C10F4 having 2,3,5,6-tetrafluorophenylene moieties were synthesized and investigated on the mesomorphic behavior. It was revealed that these exhibit a hexagonal columnar (Col(h)) phase, and this mesomorphism is quite different from the corresponding nonfluorinated homologues, C6H4 and C10H4 predominantly showing a discotic nematic (N-D) phase.