Developing polymer solar cells (PSCs) with high photovoltaic performance and mechanical robustness is one of the most urgent tasks to ensure their operational reliability and applicability in wearable devices. However,...

All‐polymer solar cells (all‐PSCs) are a highly attractive class of photovoltaics for wearable and portable electronics due to their excellent morphological and mechanical stabilities. Recently, new types of polymer acceptors (PAs) consisting of non‐fullerene small molecule acceptors (NFSMAs) with strong light absorption have been proposed to enhance the power conversion efficiency (PCE) of all‐PSCs. However, polymerization of NFSMAs often reduces entropy of mixing in PSC blends and prevents the formation of intermixed blend domains required for efficient charge generation and morphological stability. One approach to increase compatibility in these systems is to design PAs that contain the same building blocks as their polymer donor (PD) counterparts. Here, a series of NFSMA‐based PAs [P(BDT2BOY5‐X), (X = H, F, Cl)] are reported, by copolymerizing NFSMA (Y5‐2BO) with benzodithiophene (BDT), a common donating unit in high‐performance PDs such as PBDB‐T. All‐PSC blends composed of PBDB‐T PD and P(BDT2BOY5‐X) PA show enhanced molecular compatibility, resulting in excellent morphological and electronic properties. Specifically, PBDB‐T:P(BDT2BOY5‐Cl) all‐PSC has a PCE of 11.12%, which is significantly higher than previous PBDB‐T:Y5‐2BO (7.02%) and PBDB‐T:P(NDI2OD‐T2) (6.00%) PSCs. Additionally, the increased compatibility of these all‐PSCs greatly improves their thermal stability and mechanical robustness. For example, the crack onset strain (COS) and toughness of the PBDB‐T:P(BDT2BOY5‐Cl) blend are 15.9% and 3.24 MJ m–3, respectively, in comparison to the PBDB‐T:Y5‐2BO blends at 2.21% and 0.32 MJ m–3.

The development of small-molecule acceptors (SMAs) has significantly enhanced the power conversion efficiency (PCE) of polymer solar cells (PSCs); however, the inferior mechanical properties of SMA-based PSCs often limit their long-term stability and application in wearable power generators. Herein, we demonstrate a simple and effective strategy for enhancing the mechanical robustness and PCE of PSCs by incorporating a high-molecular-weight (MW) polymer acceptor ( P A , P(NDI2OD-T2)). The addition of 10–20 wt % P A leads to a more than 4-fold increase in the mechanical ductility of the SMA-based PSCs in terms of the crack onset strain (COS). At the same time, the incorporation of P A into the active layer improves the charge transport and recombination properties, increasing the PCE of the PSC from 14.6 to 15.4%. The added P A s act as tie molecules, providing mechanical and electrical bridges between adjacent domains of SMAs. Thus, for the first time, we produce highly efficient and mechanically robust PSCs with a 15% PCE and 10% COS at the same time, thereby demonstrating their great potential as stretchable or wearable power generators. To understand the origin of the dual enhancements realized by P A , we investigate the influence of the P A content on electrical, structural, and morphological properties of the PSCs.