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The development of donor-acceptor (DA) based bulkheterojunction (BHJ) polymer solar cells (PSCs) has made significant progress in the past decade. In particular, power conversion efficiency (PCE) of 8–9% in a single junction device has been demonstrated.[1–5] Among various materials developed for BHJ devices, the multifused-ring conjugated polymers are particularly interesting due to their superior optical and electrical properties.[6–20] The highly fused aromatic/heteroaromatic units enhance effective conjugation of the polymer backbone to facilitate electron delocalization. Moreover, the covalently rigidified adjacent units could prevent rotational disorder to reduce reorganization energy, which results in enhanced charge carrier mobilities.[21–23] To date, numerous fused-ring, ladder type donor systems have been developed since the first report of thiophene-phenylene-thiophene (TPT)(also called …