Extending π-conjugation of donor units in fused ring electron acceptors (FREAs) promises to reinforce intramolecular charge transfer for smaller bandgaps, and enhances intermolecular interactions for higher charge mobility. Despite these advantages, power conversion efficiencies (PCEs) of FREAs with a large planar donor core are still below 12%. Herein, a fused decacyclic donor unit, IDC, is developed, and the FREA, IDCIC, whose optical bandgap is 1.45 eV, is synthesized. The FTAZ:IDCIC-based organic solar cell (OSC) with a binary additive, chloronaphthalene and 1,8-diiodooctane (CN&DIO), affords a remarkable PCE of 13.58%, which is among the highest efficiencies of OSCs. The binary additive plays a crucial role in the morphology of FTAZ:IDCIC-based OSCs. The addition of DIO promotes IDCIC to aggregate and enhances domain size and domain purity in FTAZ:IDCIC blend film for its poor solubility in DIO, while the addition of chloronaphthalene (CN) inhibits the aggregation, facilitates IDCIC to diffuse into the donor, and reduces domain size and domain purity for its excellent solubility in CN. The binary additive, CN&DIO, compromises the effect of the two; thus FTAZ:IDCIC-based OSCs with 0.25% CN&DIO obtain moderate domain size and high domain purity simultaneously, achieving the least charge recombination for the highest JSC (21.98 mA cm−2) and fill factor (FF) (71.03%)