The supramolecular structures of new functional discotic oligomers formed on the water surface, within Langmuir-Blodgett (LB) multilayers and in the mesomorphic bulk state are described. The novel discotic oligomers are composed of triphenylene side groups attached to amino-substituted 1,3,5-triazine units in the main chain. The oligomeric triphenylenes form stable monofilms at the air-water interface with an edge-on orientation of the hydrophobic triphenylene side groups. LB multilayers are characterized by an edge-on bilayer packing with interdigitation of discotic side groups of adjacent bilayers. An unusual lamellar layer arrangement due to hydrogen bonding between the backbones is found for the bulk phase.