The formation and spectroscopic properties of quercetin (QCT)–divalent metal complexes were studied using Cu²⁺, Ni²⁺, Co²⁺, Mn²⁺, Zn²⁺, Mg²⁺, and Ca²⁺ in a hydro‐organic mixed solvent. The change of UV/visible absorption spectra of QCT due to addition of a metal showed the complex formation. The intensity of fluorescence spectra increased gradually with titration of the metal. The experimental data and theoretical calculation suggest that Cu²⁺, Ni²⁺, Co²⁺, and Mn²⁺ coordinate the site between C(3)OH and C(4)O but Zn²⁺ prefers to bind to the site between C(5)OH and C(4)O. QCT–Cu²⁺, QCT–Ni²⁺, QCT–Co²⁺, and QCT–Mn²⁺ complexes exhibit S₂ → S₀ fluorescence only as S₁ → S₀ emission is absent due to the excited‐state intramolecular proton transfer (ESIPT) at the S₁ state. As this ESIPT cannot occur at the QCT–Zn²⁺ due to the chelation of Zn²⁺ at a different site, QCT–Zn²⁺ can produce characteristic S₂ → S₀ and S₁ → S₀ dual fluorescence.