AbstractOrganic electrochemical transistors (OECTs) are of great interest owing to their potential applications in bioelectronics and neuromorphic systems. However, n‐type OECTs suffer from poor stability and facile degradation, mainly due to the oxygen reduction reactions in organic mixed ionic‐electronic conductors during device operation. In this study, a small‐molecule passivation strategy is introduced to greatly improve the stability of poly(benzobisimidazobenzophenanthroline) (BBL)‐based n‐type OECTs. 6,6‐Phenyl‐C61‐butyric acid methyl ester (PCBM) is spin‐coated onto the BBL layer to form a smooth and hydrophobic passivation layer, which effectively inhibits the oxygen reduction reactions while enabling ion permeation in aqueous electrolytes. Consequently, the OECTs employing the PCBM/BBL bilayers with an optimized PCBM thickness exhibit significantly improved operational stability at various electrolyte conditions (0.1 m NaCl or NaOH) and over a wide gate‐voltage sweep range (from −0.7 to 0.7 V). Owing to the high electron mobility of PCBM, the carrier mobility and switching speed of the PCBM/BBL OECTs are also improved compared with those of the pristine BBL OECTs. This study demonstrates the beneficial effects of simple surface passivation in organic mixed ionic‐electronic conductors and provides valuable insights for the design of high‐performance and stable OECTs for more specialized and advanced applications.