A series of novel naphthophenanthridine derivatives are synthesized via N-annulation of hexabutoxytriphenylene-1-amine with various aliphatic aldehydes through the Pictet–Spengler reaction. The synthesized derivatives have been found to self-assemble into a columnar hexagonal mesophase over a wide temperature range, as validated through polarized optical microscopy, differential scanning calorimetry and X-ray diffraction experiments. The photophysical properties of these compounds were studied using UV–visible and emission spectroscopy. The synthesized compounds exhibit ambipolar charge transport, showing temperature-independent electron and hole mobility on the order of 3 × 10–4 cm2/V s, as evaluated by the time-of-flight technique. These novel N-annulated derivatives can be of immense potential toward semiconducting applications of self-assembling supramolecular systems.