Single‐component organic solar cells based on double cable polymers have achieved remarkable performance, with DCPY2 reaching a high efficiency of over 13%. In this study, DCPY2 is further optimized with an efficiency of 13.85%, maintaining a high fill factor (FF) without compromising the short circuit current. Despite its intermixed morphology, DCPY2 shows a reduced recombination rate compared to their binary counterpart (PBDB‐T:Y‐O6). This slower recombination in DCPY2 is attributed to the reduced wavefunction overlap of delocalized charges, achieved by spatially separating the donor and acceptor units with an alkyl linker, thereby restricting the recombination pathways. Adding 1,8‐diiodooctane (DIO) into DCPY2 further reduced the recombination rate by facilitating acceptor aggregation, allowing free charges to become more delocalized. The DIO‐assisted aggregation in DCPY2 (5% DIO) is evidenced by an increased pseudo‐pure domain size of Y‐O6. Fine molecular control at the donor/acceptor interface in the double‐cable polymer achieves reduced non‐geminate recombination under efficient charge generation, increased mobility, and charge carrier lifetime, thereby achieving superior performance. Nevertheless, the FF is still limited by relatively low mobility compared to the blend, suggesting the potential for further mobility improvement through enhanced higher‐dimensional packing of the double‐cable material.