A novel approach to ambipolar semiconductors based on hydrogen-bonded complexes between a star-shaped tris(triazolyl)triazine and triphenylene-containing benzoic acids is described. The formation of 1:3 supramolecular complexes was evidenced by different techniques. Mesogenic driving forces played a decisive role in the formation of the hydrogen-bonded complexes in the bulk. All of the complexes formed by nonmesogenic components gave rise to hexagonal columnar (Col(h)) liquid crystal phases, which are stable at room temperature. In all cases, X-ray diffraction experiments supported by electron density distribution maps confirmed triphenylene/tris(triazolyl)triazine segregation into hexagonal sublattices and lattices, respectively, as well as remarkable intracolumnar order. These highly ordered nanostructures, obtained by the combined supramolecular H-bond/columnar liquid crystal approach, yielded donor/acceptor coaxial organization that is promising for the formation of ambipolar organic semiconductors with high mobilities, as indicated by charge transport measurements.