AbstractMechanical stretchability is a vital criterion for the wearable application of organic solar cells (OSCs), while the excessive rigidity of fused‐ring small molecular acceptors make the photovoltaic film hard to meet the stretchable requirements. Herein, an effective strategy is developed to construct an intrinsically stretchable active layer by inserting copolymer PM6‐b‐PYSe as an interlayer between layer‐by‐layer processed D18 and BTP‐eC9. The copolymer interlayer shunts the penetration of BTP‐eC9 and facilitates an appropriate phase separation, favoring the enhanced crack onset strain of 17.69% compared to the D18/BTP‐eC9 film (9.67%). Combining with the optimal energy levels, prolonged carrier lifetime, and suppressed bimolecular recombination aroused by the incorporation of PM6‐b‐PYSe, the D18/PM6‐b‐PYSe/BTP‐eC9‐based OSC yields an encouraging efficiency of 17.97%. In particular, the device demonstrates excellent mechanical property, which can retain over 80% after 4000 bending cycles. This work provides an effective strategy to simultaneously enhance the intrinsic mechanical stretchability and photovoltaic performance of flexible OSCs.