This paper describes the synthesis of an angular coumarinacene. Its molecular structure by single-crystal X-ray analysis is revealed for the first time, which noted a sandwich-dimeric herringbone arrangement. Its solution reveals visible absorption and bright yellow-orange emission. The pyranone-annulated angular coumarinacene is relatively stable, both thermally and photochemically, when compared to popular acenes. Its alignment of frontier orbital energy levels dictates its possible entry into electronics. © 2021 Wiley-VCH GmbH