A curved sp 2 carbon scaffold containing fused pentagon and heptagon units (1) was synthesized by Pdcatalyzed [5+2] annulation from a 3,9-diboraperylene precursor and shows two reversible oxidation processes at low redox potential, accompanied by a butterfly-like motion. Stepwise oxidation produced radical cation 1C + and dication 1 2+. In the crystal structure, 1 exhibits a chiral cisoid conformation and partial p-overlap between the enantiomers. For the radical cation 1C + , a less curved cisoid conformation is observed with a p-dimer-type arrangement. 1 2+ adopts a more planar structure with transoid conformation and slip-stacked p-overlap with closest neighbors. We also observed an intermolecular mixed-valence complex of 1•(1C +) 3 that has a huge trigonal unit cell [(1) 72 (SbF 6) 54 •(hexane) 101 ] and hexagonal columnar stacks. In addition to the conformational change, the aromaticity of 1 changes from localized to delocalized, as demonstrated by AICD and NICS(1) zz calculations.