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The benefits of flavonoids on human health are very often ascribed to their potential ability to act diminishing free radical steady state concentration in biological systems providing antioxidant protection. This is an assumption based on the chemical structures of flavonoids that support their capacity to scavenge free radicals and chelate redox-active metals. In this paper we will use thermodynamic and kinetic approaches to analyze the interactions of flavonoids with biological material and from there, extrapolate the physiological relevance of their antioxidant actions. Thermodynamic analysis predicts that both, scavenging of oxygen-derived radicals and the sequestration of redox-active metals are energetically favored. Nevertheless, the actual concentrations reached by flavonoids in most animal and human tissues following dietary ingestion are incompatible with the kinetic requirements necessary to reach reaction …