High‐performance polymer donors when paired with nonfullerene acceptors are mainly limited to flanking halogenated benzodithiophene (BDT)‐based π‐conjugated copolymers, which however involve the complex synthetic procedures. Herein, we developed 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. Compared with the benchmark PBDB‐T donor containing BDD unit, additional incorporation of 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 PCE of 10.28% is thus obtained in the optimal P75 (BDD : DPP = 3 : 1 mol%) and Y6 blend cells in comparison to 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 boost 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 enhances JSC and FF in device, respectively.