Flavonoids and coumaric acid derivatives were identified from dandelion flower (Taraxacum officinale). Characteristics of chain-breaking antioxidants, such as extended lag phase and reduced propagation rate, were observed in oxidation of linoleic acid emulsion with the addition of dandelion flower extract (DFE). DFE suppressed both superoxide and hydroxyl radical, while the latter was further distinguished by both site-specific and non-specific hydroxyl radical inhibition. DPPH-radical-scavenging activity and a synergistic effect with alpha-tocopherol were attributed to the reducing activity derived from phenolic content of DFE. A significant (p < 0.05) and concentration-dependent, reduced nitric oxide production from acterial-lipopolysaccharide-stimulated mouse macrophage RAW264.7 cells was observed with the addition of DFE. Moreover, peroxyl-radical-induced intracellular oxidation of RAW264.7 cells was inhibited significantly (p < 0.05) by the addition of DFE over a range of concentrations. These results showed that the DFE possessed marked antioxidant activity in both biological and chemical models. Furthermore, the efficacy of DFE in inhibiting both reactive oxygen species and nitric oxide were attributed to its phenolic content.