The interactions of Hemoglobin (Hb) with different metal ions were studied by fluorescent spectra.It showed that Zn 2+ can improve the fluorescent intensity of Hb,Cu 2+ can quench fluorescence of Hb,and Ag + can quench weakly fluorescence of Hb.When the mixed ions was added into Hb solution, the spectra of Hb revealed obvious difference between separate ion and mixed ions, which resulted in competitive coordination effect or synergetic effect in the coexistent ions system.