Two thermally and water stable zinc-based coordination polymers (CPs) [Zn2(bb)(AZA)2]n (1) and [Zn2(bb)(PA)2]n (2) (bb = 4,4′- bis (imidazolyl) biphenyl, H2AZA=Azelaic acid and H2PA=Heptanedioic acid) were synthesized by a hydrothermal method and were structurally characterized through X-ray single-crystal diffraction, X-ray powder diffraction, elemental analysis, thermogravimetric analysis, infrared spectroscopy, ultraviolet spectroscopy, and other tests. Both of CPs 1 and 2 have 2D layered networks. Notably, CP 1 behaves as a multi-responsive fluorescent sensor toward dinotefuran (DTF) and 2,4,6-trinitrophenol (TNP) with high sensitivity, selectivity, and stability based on high fluorescence quenching efficiency. The detection limits for dinotefuran (DTF) and 2,4,6-trinitrophenol (TNP) were determined to be 1.99 ppm and 3.19 ppm, respectively. Additionally, the color of the test paper remained unchanged under natural light. Furthermore, the possible sensing mechanisms have been discussed in detail, and are supported by PXRD analysis, UV–vis spectroscopy, and density functional theory (DFT).