We report the synthesis and characterization of two series of novel triphenylene-based benzene-bridged symmetric discotic dimers. Two triphenylene discotics have been connected to a rigid benzene ring via flexible methylene spacers. In one series, triphenylene moiety was tethered with benzene via an ester linkage, while in the second series it is via an ether linkage. Within each series, the orientation of the linkage of the triphenylene core around the benzene core has been changed by substituting the benzene ring at o-, m-, and p-positions. These materials have been characterized from their spectral and elemental analysis. The thermotropic liquid crystalline properties were investigated by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction studies. All the virgin compounds do not display any mesomorphism; however, their charge transfer complexes with trinitrofluorenone, an electron acceptor, exhibited columnar mesophases. The direct current (de) conductivity of charge transfer complexes at two ratios has been studied at variable temperature. The small conductivity value demonstrates that long spacers as well as connectivity to the rigid benzene ring dilute the column packing, hence making pi-pi interaction less efficient for the entire column length. A hexagonal assembly of triphenylene-benzene dimer 12 on a highly oriented pyrolytic graphite (HOPG) surface has been visualized with scanning tunneling microscopy (STM).