Copyright © 2019 American Chemical Society. An antiaromatic cation of the expanded hexapyrrolohexaazacoronene (HPHAC) 1+ was synthesized by a Vilsmeier-type reaction of the partially unfused HPHAC 2. X-ray diffraction analysis revealed the formation of a seven-membered ring with a methyne linkage between the pyrrole moieties. Although 1+ is a monocation, upfield shifts of the peripheral ethyl protons were clearly observed in the 1H NMR spectra, indicating 24πantiaromaticity. Global antiaromaticity was also supported by nucleus-independent chemical shift and anisotropy of the induced current density calculations. Cation 1+ displayed two reversible oxidations and one irreversible reduction in the cyclic voltammetry measurements. Treatment of 1+ with NOSbF6 gave aromatic trication 13+ with 22π-electron conjugation.