Zinc(II) enhances radical scavenging of the flavonoid kaempferol (Kaem) most significantly for the 1:1 Zn(II)-Kaem complex in equilibrium with the 1:2 Zn(II)Kaem complex both with high affinity at 3-hydroxyl and 4-carboxyl coordination. In methanol/chloroform (7/3, v/v), 1:1 Zn(II)-Kaem complex reduces beta-carotene radical cation, beta-Car center dot+, with a second beta-order rate constant, 1.88 x 10(8) L. mol(-1).s(-1), while both Kaem and 1:2 Zn(II)-Kaem complex are nonreactive, as determined by laser flash photolysis. In ethanol, 1:1 Zn(II)-Kaem complex reduces the 2,2-diphenyl-1-picrylhydrazyl radical, DPPH center dot, with a second-order rate constant, 2.48 X 10(4) L.mol(-1).s(-1), 16 times and 2 times as efficient as Kaem and 1:2 Zn(II)-Kaem complex, respectively, as determined by stopped-flow spectroscopy. Density functional theory calculation results indicate significantly increased acidity of Kaem as ligand in 1:1 Zn(II)-Kaem complex other than in 1:2 Zn(II)-Kaem complex. Kaem in 1:1 Zn(II)-Kaem complex loses two protons (one from 3-hydroxyl and one from phenolic hydroxyl) forming 1:1 Zn(II)-(Kaem-2H) during binding with Zn(II), while Kaem in 1:2 Zn(II)-Kaem complex loses one proton in each ligand forming Zn(II)-(Kaem H)(2), as confirmed by UV-vis absorption spectroscopy. Zn(II)-(Kaem-2H) is a far stronger reductant than Kaem and Zn(II)-(Kaem H)(2) as determined by cyclic voltammetry. Significant rate increases for the 1:1 complex in both beta-Car center dot(+) scavenging by electron transfer and DPPI-I center dot scavenging by hydrogen atom transfer were ascribed to decreases of ionization potential and of bond dissociation energy of 4'-OH for deprotonated Zn(II)-(Kaem-2H), respectively. Increased phenol acidity of plant polyphenols by 1:1 coordination with Zn(II) may explain the unique function of Zn(II) as a biological antioxidant and may help to design nontoxic metal-based drugs derived from natural bioactive molecules.