Synthesis and characterization of doubly diphenylene-fused 2,3,6,7-tetraazanaphthalene 1 are described. Single-crystal X-ray diffraction analysis showed the highly twisted structure of 1 with a degree of twisting of 13.0°/Å, which is one of the largest values for a π-system. In the crystal, molecules of 1 formed an orthogonal one-dimensional column with π-stacking of diphenylene moieties and a short intermolecular C···N distance due to lone-pair/π* interaction, which is a rare example of lone-pair/π* interaction in a supramolecular assembly.