The first synthesis of a series of substituted trinaphthylene derivatives via a palladium-catalyzed aryne cyclotrimerization is reported. This method provides an approach for the preparation of novel disk-shaped polycyclic aromatic hydrocarbons that self-assemble via π−π interactions and may form columnar liquid crystal phases. Although the trinaphthylenes prepared in this study do not exhibit columnar mesophases, variable concentration 1H NMR studies provide evidence for aggregation in solution.