We report the synthesis of novel polycatenar dibenzopentacenequinones 1 and 2 that are designed to form columnar liquid crystalline phases. The mesomorphic properties of these compounds were investigated by polarized optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. While compound 1 exhibits two distinct columnar mesophases between 148 and 177 °C, fluorinated 2 exhibits a columnar mesophase from 121 to 336 °C. This dramatic stabilization of the columnar mesophase of 2 can be attributed to improved π-stacking as a result of arene-perfluoroarene interactions.