Catalytic hydrogenation reduction based on sodium borohydride (NaBH ) has gained attention as an appealing "one-stone-two-birds" approach for the simultaneous elimination of nitroaromatic pollutants and the production of high-value aminoaromatics under mild conditions. However, the slow kinetics of NaBH dissociation on the surface of catalysts restrict the catalytic hydrogenation reduction efficiency. Herein, we report an intelligent localized sulfidation strategy for an in situ implantation of Bi S nanorods within quasi-Bi-MOF architectures (Bi S @quasi-Bi-MOF) by fine-tuning the pyrolysis temperature. In this novel Bi S @quasi-Bi-MOF, the porous quasi-Bi-MOF enables efficient adsorption of BH and 4-nitrophenol (4-NP), while Bi S facilitates the BH dissociation to form H * species adsorbed on the catalyst surface. Benefiting from the synergistic structure, Bi S @quasi-Bi-MOF exhibits excellent performance for the catalytic reduction of 4-NP, delivering a high turnover frequency (TOF) of 1.67 × 10 mmol mg min and an extremely high normalized rate constant ( ) of 435298 s g . The kinetic analysis and electrochemical tests indicate that this catalytic hydrogenation reduction follows the Langmuir-Hinshelwood mechanism. This study enriches the synthetic strategy of MOF-based derivatives and offers a new catalytic platform for hydrogenation reduction reactions.