<p>Vanillin (VAN), potassium sorbate (PS) and Na⁺ are widely used additives in food, which all play important roles in human health. Therefore, the efficient detection of VAN, PS and Na⁺ is crucial for food safety and human health. In this work, a new heterometallic Zn-Tb coordination cluster compound, namely, [Zn₂Tb₂(DCA)₁₀(2,2’-bpy)₂] (<b>1</b>) (DCA = 3,5-dichlorobenzoic acid, 2,2’-bpy = 2,2’-bipyridine) has been hydrothermally synthesized and explored as fluorescent sensor for detection of VAN, PS and Na⁺. Compound <b>1</b> displays a tetranuclear Zn₂Tb₂ cluster structure with linear Zn···Tb···Tb···Zn arrangement, which exhibits excellent fluorescent stability in water. The fluorescent sensing investigations indicate that <b>1</b> can detect VAN, PS and Na⁺ in water with superior selectivity and sensitivity. The limits of detection (LOD) toward VAN, PS and Na⁺ are 61 nM, 67 nM and 320 nM, respectively. More importantly, <b>1</b> can also be used for the detection of VAN in milk powder, PS in oyster sauce and Na ⁺ in tap water. The possible sensing mechanisms for VAN, PS and Na⁺ were further discussed via experimental and theoretical studies. Moreover, the fluorescent films of <b>1</b> were prepared for the visual detection of VAN, PS and Na⁺, which facilitates the convenient application of <b>1</b>. All these results suggest the potential application of <b>1</b> as multifunctional sensor of VAN, PS and Na⁺.</p>