<p>High-efficiency degradation and immediate detection of organophosphorus (OPs) nerve agents under realistic, dry conditions are of paramount significance in emerging applications. While the synthetic integration of these two distinct functions within a single material platform remains a big challenge, it is highly desirable. Herein, by mimicking phosphotriesterase’s active site and applying the lanthanides (Ln³⁺) luminescence mechanism, bifunctional materials <b>Im-Ln@MOF-808</b> (Ln = Eu/Tb) are designed that enable visual recognition and detoxification of a nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP), under ambient, unbuffered, and solvent-free conditions. The metallization of the Zr₆-oxo clusters of MOF-808 with Ln³⁺ allows for exhibiting intense fluorescence in the solid state. Notably, the ingeniously introduced Im not only provides OH⁻ for nucleophilic attack and regenerates catalytically active Zr₆ sites during the hydrolysis but also dramatically enhances the 4f-5d transition probabilities and the radiative transition rate of Ln³⁺. After contact with OPs, obvious fluorescence quenching happens by the dissociation of Ln–Im bonds, with a sensitive fluorescence quenching response with detection limits as low as 0.328 and 0.168 µM, respectively. This work illustrates, for the first time, the feasibility of simultaneous fluorescence detection and solid-phase decontamination of nerve agents using a single material, providing new insights for developing practical protective countermeasures.</p>