Easily producible sensors for harmful industrial waste compounds are of significant interest for both human health and the environment. Three novel coordination polymers, [Ag(μ-aca)(μ4-bztpy)1/2] (1), [Ag(μ-bza)(μ-bpa)] (2), and [Ag2(μ-aca)2(μ-bpa)2]·EtOH·2H2O (3), were assembled in this study by reactions using Ag+ as a node with the pyridyl ligand 1,2,4,5-tetrakis(4-pyridyl)benzene (bztpy) or 9,10-bis(4-pyridyl)anthracene (bpa) and an auxiliary chelating carboxylic ligand. Single-crystal X-ray structural analyses revealed that compound 1 has a 3D framework consisting of 1D [Ag(aca)]∞ chains and bztpy linkers, while 2 and 3 have 2D layered structures consisting of binuclear Ag-carboxylate units and bpa linkers, respectively. Topological studies revealed that 1 has a bbf topology, while 2 and 3 are 2D [4,4] rhombic grids. The compounds were further characterized by powder X-ray diffraction, IR, elemental analysis, thermogravimetric analysis, and a luminescence study. The solids of 1-3 exhibited intense photoluminescent emission with λemmax at ca. 493, 472, and 500 nm, respectively. Remarkably, due to their excellent framework stability, 1 and 2 can act as multiresponsive luminescent sensors for nitrobenzene, Fe3+, and Cr2O72- with a high selectivity and sensitivity ascribed to their quenching effect.