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Dodecaphenyltetracene (4), the largest perphenylacene yet prepared, was synthesized from known tetraphenylfuran, hexaphenylisobenzofuran, and 1,2,4,5‐tetrabromo‐3,6‐diphenylbenzene in three steps. The X‐ray structure of the deep red, highly luminescent 4 shows it to be a D₂‐symmetric molecule with an end‐to‐end twist of 97°. The central acene is encapsulated by the peripheral phenyl substituents, and as a result, the molecule is relatively unreactive and even displays reversible electrochemical oxidation and reduction.