A new one-dimensional double chain photoluminescent Hg(II) coordination polymer (CP), {[Hg(L)2]·(ClO4)2}n (1), was synthesized using a benzimidazole-appended tripodal tridentate ligand, 1,3,5-tris(benzimidazolylmethyl)benzene (L). The dynamic and flexible framework of 1 allows it to be entitled as first Hg(II)-based CP belonging to the rare category of CPs that exhibit multistimuli-responsive photoluminescence sensing properties and called as "smart" material. The sensitivity of this material via luminescence quenching method showing "turn off" behavior to a range of stimuli, including anions, solvents, and nitroaromatic compounds (NACs), offers more fine-grained control over its properties. 1 can easily adjust its channel dimensions to encapsulate different guest anions forming complete/partial anion-exchanged materials 1A-1B/1C-1E using NO3 -, BF4 -, OTf-, OTs-, and PF6 - anions, respectively. Reversible (1A and 1B) and irreversible (1C-1E) anion exchange behaviors were observed for the complete and partial anion-exchanged products, respectively. The noteworthy feature of the anion-exchanged compounds is their anion-triggered luminescent behavior depending on different properties of anions.The excellent emission in water and high hydrolytic stability of 1 allows its use for rapid and efficient fluorescence-based detections of NACs in aquatic system. The uncoordinated pendant benzimidazole moiety in 1 serves as Lewis basic recognition site for trinitrophenol (TNP) detection, and along with electron- and energy-transfer mechanisms, 1 forms a luminescent probe for detection of TNP with low detection limits (0.55 ppm), exhibiting excellent photostability and recyclability. 1 also represents the first reported Hg(II)-based sensory CP material that can discriminate nitrophenol and nitroaniline isomers through fluorescence sensing. © 2018 American Chemical Society.