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Emerging wearable devices would benefit from integrating ductile photovoltaic light-harvesting power sources. In this work, we report a small-molecule acceptor (SMA), also known as a non–fullerene acceptor (NFA), designed for stretchable organic solar cell (s-OSC) blends with large mechanical compliance and performance. Blends of the organosilane-functionalized SMA BTP-Si4 with the polymer donor PNTB6-Cl achieved a power conversion efficiency (PCE) of >16% and ultimate strain (ε_u) of >95%. Typical SMAs suppress OSC blend ductility, but the addition of BTP-Si4 enhances it. Although BTP-Si4 is less crystalline than other SMAs, it retains considerable electron mobility and is highly miscible with PNTB6-Cl and is essential for enhancing ε_u. Thus,s-OSCs with PCE > 14% and operating normally under various deformations (>80% PCE retention under an 80% strain) were demonstrated. Analysis of several SMA-polymer blends revealed general molecular structure–miscibility–stretchability relationships for designing ductile blends.