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The effective detection of environmental pollutants is very important to the sustainable development of human health and the environment. A luminescent Cd(II) coordination complex, {[Cd(dbtdb)(1,2,4-H₃btc)]·0.5H₂O}<i>_n</i> (<b>1</b>) (dbtdb = 1-(2,3,5,6-tetramethyl-4-((2-(thiazol-4-yl)-2H-benzo[d]imidazol-3(3aH)-yl)methyl)benzyl)-2,7a-dihydro-2-(thiazol-4-yl)-1H-benzo[d]imidazole, 1,2,4-H₃btc = 1,2,4-benzenetricarboxylic acid), was obtained by hydrothermal reactions. Complex <b>1</b> has a chain structure decorated with uncoordinated Lewis basic O and S donors and provides good sensing of Fe³⁺, Cr₂O₇²⁻, and <i>p</i>-nitrophenol with fluorescence quenching through an energy transfer process. The calculated binding constants were 3.3 × 10³ mol⁻¹ for Fe³⁺, 2.36 × 10⁴ mol⁻¹ for Cr₂O₇²⁻, and 9.3 × 10³ mol⁻¹ for <i>p</i>-nitrophenol, respectively. These results show that <b>1</b> is a rare multiresponsive sensory material for efficient detection of Fe³⁺, Cr₂O₇²⁻, and <i>p</i>-nitrophenol.