An unsymmetrically substituted triphenylene, with two adjacent chloroethoxyethyl lateral flexible chains, was synthesized and characterized. Although this compound showed no mesomorphic behavior, it formed a donor acceptor charge-transfer complex with 2,4,7-trinitrofluorenone (TNF). The resulting I: I complex has been investigated using UV-vis and IR spectroscopy, optical microscopy, thermal analysis, and X-ray diffraction. A columnar mesophase with hexagonal symmetry was found. More interestingly, this charge-transfer complex can be easily aligned on a glass surface in a homeotropic orientation, which is stable at room temperature (RT) and over a wide temperature range.