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 Fe3+, 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 Fe3+. 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.