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Conjugation-break flexible spacers in-between π-conjugated segments were utilized herein toward processable perylene diimide (PDI)-based polymers. Aromatic-aliphatic PDI-based polymers were developed via the two-phase polyetherification of a phenol-difunctional PDI monomer and aliphatic dibromides. These polyethers showed excellent solubility and film-forming ability and deep lowest unoccupied molecular orbital (LUMO) levels (-4.0 to -3.85 eV), indicating the preservation of good electron-accepting character or characteristics, despite