The development of high‐performance organic solar cells (OSCs) with high operational stability is essential to accelerate their commercialization. Unfortunately, our understanding of the origin of instabilities in state‐of‐the‐art OSCs based on bulk heterojunction (BHJ) featuring non‐fullerene acceptors (NFAs) remains limited. Herein, we developed NFA‐based OSCs using different charge extraction interlayer materials and studied their storage, thermal, and operational stabilities. Despite the high power conversion efficiency (PCE) of the OSCs (17.54%), we found that cells featuring self‐assembled monolayers (SAMs) as hole‐extraction interlayers exhibited poor stability. The time required for these OSCs to reach 80% of their initial performance (T₈₀) was only 6 h under continuous thermal stress at 85 °C in a nitrogen atmosphere and 1 h under maximum power point tracking (MPPT) in a vacuum. Inserting MoO_x between ITO and SAM enhanced the T₈₀ to 50 and ~15 h after the thermal and operational stability tests, respectively, while maintaining a PCE of 16.9%. Replacing the organic PDINN electron transport layer with ZnO NPs further enhances the cells' thermal and operational stability, boosting the T₈₀ to 1000 and 170 h, respectively. Our work reveals the synergistic roles of charge‐selective interlayers and device architecture in developing efficient and stable OSCs.