The violation of the Kasha photoemission rule in organic molecules has intrigued chemists since their discovery, being always of relevance given its connection with unique electronic properties of molecules. However, an understanding of the molecular structure–anti-Kasha property relationship in organic materials has not been well-established, possibly because of the few existing cases available, limiting their prospective exploration andad hocdesign. Here we introduce a novel strategy to design organic emitters from high excited states combining intramolecularJ-coupling of anti-Kasha chromophores with the hindering of vibrationally-induced non-radiative decay channels by enforcing molecular rigidity. We apply our approach to the integration of two antiparallel azulene units bridged with one heptalene all inserted into a polycyclic conjugated hydrocarbon (PCH). With the help of quantum chemistry calculations, we identify a suitable PCH embedding structure and predict its anti-Kasha emission from the third high energy excited singlet state. Finally, steady fluorescence and transient absorption spectroscopy studies corroborate the photophysical properties in a recently synthesized chemical derivative with this pre-designed structure.