A new Ni(II) compound [Ni(bim)2(H2O)4] (1,5-nds).(H2O)0.5 1 (bim = benzimidazole, 1,5-nds-Na = disodium 1,5-naphthalenedisulfonate) was readily synthesized at room temperatureAlthough compound 1 is only a mononuclear compound, it is extended into a 2D supermol. layer by hydrogen bonding interactions.Hirshfeld surfaces and fingerprint maps of compound 1 crystal packing were calculated to gather information on non-covalent interactions.Photoluminescence experiments showed that 1 not only possessed good solid-state fluorescence performance but also favorable fluorescence characteristics and stability in aqueous solutions, which can be exposed to acidic and alk. environmental conditions (pH = 1-14) for a long time.Remarkably, compound 1 displayed outstanding anti-interference properties, high sensitivity, high quenching rate, and low limit of detection (LOD) against acetylacetone (acac), MnO-4, and tetracycline (TET) in water media via the Turn-Off effect (LOD:7.03 μM for acac, 2.92 μM for MnO-4 and 0.65 μM for TET).Especially, compound 1 can also be used as a rare ratiometric fluorescent probe for the detection of Ag+ down to the nM level.The exceptional multi-responsive performance suggested that compound 1 could be a potential multifunctional sensor.Furthermore, possible mechanisms were systematically investigated.