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Instability of silver nanowire (AgNW) has been regarded as a major obstacle to its practical applications in optoelectrical devices as transparent electrodes. Physical barrier layers such as polymer, metal, and graphene have been generally employed to improve the stability of AgNW in previous study. Herein, we first report self-assembled organothiols as an inhibitor for AgNW to achieve an overall enhancement in antioxidation, antisulfidation, thermal stability, and anti-electromigration. The self-assembled monolayers (SAMs) of phenyl azoles, methoxy silane, and methyl alkane were formed on the surface of AgNW via Ag–S covalent bond as barrier layers which provided protective effects against corrosives (e.g., O₂, H₂S). In particular, the decoration of 2-mercaptobenzimidazole (MBI) offered the best resistance to H₂S and excellent stability under a high-temperature and high-humidity environment (85 °C and 85 RH …