Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64% Efficiency All Polymer Solar Cells

All‐polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (PDs) and polymer acceptors (PAs) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three PAs, namely PBTPICm‐BDD, PBTPICγ‐BDD and PBTPICF‐BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y‐typed non‐fullerene small molecular acceptors (NF‐SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the PD being interspersed into the acceptor material, which improve the solubility between the PD and PA. The PBTPICγ‐BDD and PBTPICF‐BDD displayed better miscibility with PBQx‐TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50% and 17.17% were achieved for PBQx‐TCl:PBTPICγ‐BDD and PBQx‐TCl:PBTPICF‐BDD devices, respectively. With the addition of PYF‐T‐o as the third component into PBQx‐TCl:PBTPICγ‐BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64% was realized finally.