High‐performance polymer donors when paired with nonfullerene acceptors are mainly limited to flanking halogenated benzodithiophene (BDT)‐based π‐conjugated copolymers, which however involve complex synthetic procedures. Herein, a series of halogen‐free polymer donors that link BDT moiety with two highly electron‐deficient benzodithiophene‐dione (BDD) and diketopyrrolopyrrole (DPP) units with various molar ratios is developed. Compared with the benchmark PBDB‐T donor containing BDD unit, additional incorporation of a stronger electron‐negative DPP unit markedly lowers frontier molecular orbital levels and extends optical absorption, potentially leading to simultaneously enhanced VOC and JSC in organic solar cells. A remarkable power conversion efficiency (PCE) of 10.28% is thus obtained in the optimal P75 (BDD : DPP = 3:1 mol%) and Y6 blend cells in comparison with the reference PBDB‐T:Y6 (9.20%). A slight addition of PC71BM into the blend is found to further generate finer phase‐separated domains and thus increase the best efficiency up to 12.20%. The subtly critical roles of PC71BM are determined by transient absorption measurements on both thin‐film and in situ devices to be the prolonged free charge carrier lifetime and the shallow charge transfer states, which enhance JSC and fill factor in the device, respectively.

N-type doping of the bulk-heterojunction layer in nonfullerene organic solar cells allows to effectively ameliorate inferior electron transportation by filling traps and optimizing electron pathways, leading to a better balance...