The K₄ structure was theoretically predicted for trivalent chemical species, such as sp² carbon. However, since attempts to synthesize the K₄ carbon have not succeeded, this allotrope has been regarded as a crystal form that might not exist in nature. In the present work, we carried out electrochemical crystallization of the radical anion salts of a triangular molecule, naphthalene diimide (NDI)-Δ, using various electrolytes. X-ray crystal analysis of the obtained crystals revealed the K₄ structure, which was formed by the unique intermolecular π overlap directed toward three directions from the triangular-shape NDI-Δ radical anions. Electron paramagnetic resonance and static magnetic measurements confirmed the radical anion state of NDI-Δ and indicated an antiferromagnetic intermolecular interaction with the Weiss constant of θ = −10 K. The band structure calculation suggested characteristic features of the present material, such as a metallic ground state, Dirac cones, and flat bands.