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In this work, a new porous Zr-based metal-organic framework (MOF) with a large Brunner-Emmet-Teller (BET) surface area was prepared by the solvothermal method using 4,4'-(naphthalene-1,4-diyl)dibenzoic acid (NDDA) as the organic ligand, and the luminescent detection performance was studied systematically. The experiments combing with computations indicate that the as-synthesized material can sensitively and selectively detect nitro explosives and metal ions, especially for 2,4,6-trinitrophenol (TNP) and Fe 3＋ , due to the possible electron transfer from inorganic moieties to organic moieties with naphthalene part. Interestingly, owing to its high porosity and large surface area, this Zr-MOF showed quick luminescent response time (in 1 min) for TNP and Fe 3＋ . The results obtained may provide useful information for the design of MOFs with the large permanent porosity in sensing applications for large molecules in the future.