A new Zn(II)-based coordination polymer (1) comprising the Schiff base ligand obtained by the condensation of 5-aminosalicylic acid and salicylaldehyde has been synthesized. This newly synthesized compound has been characterized by analytical and spectroscopic methods, and finally, by single-crystal X-ray diffraction technique in this study. The X-ray analysis reveals a distorted tetrahedral environment around the central Zn(II) center. This compound has been used as a sensitive and selective fluorescent sensor for acetone and Ag+cations. The photoluminescence measurements indicate that in the presence of acetone, the emission intensity of1displays quenching at room temperature. However, other organic solvents caused meagre changes in the emission intensity of1. Additionally, the fluorescence intensity of1has been examined in the presence of different ketones viz. cyclohexanone, 4-heptanone, and 5-nonanone, to assess the interaction between the C=O group of the ketones and the molecular framework of1. Moreover,1displays a selective recognition of Ag+in the aqueous medium by an enhancement in its fluorescence intensity, representing its high sensitivity for the detection of Ag+ions in a water sample. Additionally,1displays the selective adsorption of cationic dyes (methylene blue and rhodamine B). Hence,1showcases its potential as an excellent luminescent probe to detect acetone, other ketones, and Ag+with an exceptional selectivity, and displaying a selective adsorption of cationic dye molecules.