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© 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.Extension of a fused aromatic ring core is beneficial for enhancing the intramolecular charge transfer and effective π-conjugation in A-D-A type non-fullerene acceptors (NFAs). In this work, a novel strategy involving extension of fused-ring core by symmetrically replicating core unit was developed, and a novel symmetric fused-12-ring NFA, LC81 was synthesized. When paired with the wide-bandgap polymer donor, PBT1-C, the corresponding organic solar cells (OSCs) showed a high-power c