Solid-state reactions have appealed to the organic synthetic field due to their simplicity, efficiency, and selectivity compared to liquid-phase reactions. Herein, the superstructure was realized by the solid-state reaction which converted single-crystal-to-single-crystal. The superstructure of 5,5′,5′′-(1,3,5-triazine-2,4,6-triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5-tricyanobenzene (TCB) single crystals. The TIPN superstructure was determined by single crystal X-ray diffraction and visualized by transmission electron microscopy. As the results, the superstructure has hexagonally packed 1-dimensional (1D) channels along the crystal axis. Furthermore, the superstructure arises from interdigitated nitrile interactions in the crystal lattice, and thus has electron-beam tolerance and high thermal stability.