A multifunctional fluorescent sensor Zn-MOF was successfully prepared by hydrothermal reaction, Zn²⁺ as node, 1,3,5-tris(1-imidazolyl)-benzene (L) and chiral ligands D(+)-camphoric acid (D-H₂cam) as linkers. It had been characterized by single crystal X-ray diffraction (XRD), powder X-ray diffraction (PXRD), circular dichroism (CD), chromaticity coordinates (CIE) and thermogravimetric analysis (TGA). The study of fluorescence properties revealed that the multifunctional fluorescent sensor Zn-MOF exhibited high selectivity and sensitivity to detect HSO₄⁻ or glutamate (Glu)/aspartic (Asp) by “Turn Off” the emission. Furthermore, the in situ generated [Zn-MOF + Glu/Asp] system was used for the relay detection of arginine (Arg)/lysine (Lys) without separation and purification and exhibited a new fluorescence “Turn On” signal under the same conditions. In addition, the sensing process possessed out-standing cost-saving, rapid responsiveness as well as recyclability in aqueous solution.