We report herein the synthesis of an unprecedented isomer of perylene, dicyclohepta[cd,fg]-as-indacene bearing two phenyl groups (1-Ph) by the nickel-mediated intramolecular homocoupling of a 4,4'-biazulene derivative (2). The X-ray crystallographic analysis and theoretical calculations revealed that 1-Ph adopts a unique helically twisted geometry although the local aromaticity of azulene moieties was preserved. The double covalent linkage of the two azulene skeletons imparts significant orbital interaction, which affords near-infrared (NIR) absorption (up to 1720 nm) and remarkable redox behaviors despite its closed-shell electronic structure. The optical band gap of 1-Ph is calculated to be 0.72 eV from its absorption onset, which is one of the narrowest values among the hitherto reported air-stable non-benzenoid PAHs. Furthermore, the thin-film of 1-Ph serves as a p-type semiconductor. Our study offers fundamental insights into not only the aromaticity with the nonalternant topologies of 1-Ph but also its potential application in novel organic electronics.