AbstractA new metal‐organic framework (MOF) compound, [Ni(L)(IDC)(H2O)] ⋅ 0.5 L (1), (H2IDC=4,4′‐iminodibenzoic acid), was synthesized by solvothermal reaction of 2,6‐di(1H‐imidazol‐1‐yl)naphthalene (L) and dicarboxylic acid ligands with nickel salt. The results of single crystal diffraction show that the framework belongs to the P21/c space group and has a unique infinite one‐dimensional (1D) chain structure. They are further linked together through imidazole interaction and finally form a three‐dimensional (3D) structure. The crystal structure was characterized by Powder X‐ray diffraction (PXRD), thermogravimetric analyses (TGA), infrared spectra (IR) and elemental analyses (EA). Meanwhile, the thermal stability and luminescence properties of the crystal were tested. It was found that 1 could recognize acetone molecules by luminescence quenching. It has proved itself an efficient sensor for acetone at low con‐centration.