We report the synthesis, structural characterization, and optoelectronic properties of a highly electron-deficient bi(cyclopropylidene)-framework (CN8CP2). The developed one-pot synthesis gives access to the dianionic species via thermally induced homocoupling of an iodinated precursor. The controlled oxidation yields the radical anion, whereas the neutral molecule is accessible only as an electrochemically generated in situ species. Single-crystal X-ray diffraction studies of the dianion reveal molecular layers separated by counterions, thereby enabling fluorescence in the solid state. The structure of the radical anion reveals a highly ordered arrangement of π-stacked molecules. Optical spectroscopy and quantum chemical calculations indicate that the vibronic fine structure is governed by the vibrational modes of the cyclopropane core. The analysis of the electronic structures confirms extensive spin delocalization for the radical anion and a pronounced σ-aromatic character. The exceptionally low energy levels of the acceptor orbitals are determined as −5.66 eV for the radical anion and −6.18 eV for the neutral species. Consequently, charge transfer to the neutral molecule or the radical anion results in the formation of the closed-shell dianion, which circumvents instabilities that are associated with open-shell species formed for conventional electron acceptors. Thus, CN8CP2 appears as one of the strongest small-molecule organic acceptors for advanced organic electronic materials.