Small molecule acceptor (SMA)-based organic solar cells (OSCs) have achieved high power conversion efficiencies (PCEs), while their long-term stabilities remain to be improved to meet the requirements for real applications. Herein, we demonstrate the use of donor−acceptor alternating copolymer-type compatibilizers (DACCs) into high-performance SMA-based OSCs, enhancing their PCE, thermal stability, and mechanical robustness simultaneously. The addition of DACCs to polymer donor (PD)–SMA blends effectively reduces PD–SMA interfacial tensions and stabilizes the interfaces, preventing the coalescence of the phase-separated domains. As a result, desired morphologies with high thermal stability and mechanical robustness are obtained for the PD–SMA blends. The addition of 20 wt% DACCs affords OSCs with a PCE of 17.1% and a cohesive fracture energy (Gc) of 0.89 J m–2, higher than those (PCE= 13.6% and Gc= 0.35 J m–2) for the control OSCs without DACCs. Moreover, at an elevated temperature of 120 °C, the OSCs with 20 wt% DACC exhibit excellent thermal morphological stability, retaining over 95% of the initial PCE after 300 hr.