Detailed kinetic studies have been performed for reactions of aroxyl (ArO(•)) and α-tocopheroxyl (α-Toc(•)) radicals with five catecholamines (CAs) (dopamine (DA), norepinephrine (NE), epinephrine (EN), and 5- and 6-hydroxydopamine (5- and 6-OHDA)) and two catechins (epicatechin (EC) and epigallocatechin gallate (EGCG)) to clarify the free-radical-scavenging activity of CAs. Second-order rate constants (ks and kr) for reactions of ArO(•) and α-Toc(•) radicals with the above antioxidants were measured in 2-propanol/water (5:1, v/v) solution at 25.0 °C, using single- and double-mixing stopped-flow spectrophotometries, respectively. Both the rate constants (ks and kr) increased in the order NE < EN < DA < EC < 5-OHDA < EGCG < 6-OHDA. The ks and kr values of 6-OHDA are large and comparable to the corresponding values of ubiquinol-10 and sodium ascorbate, which show high free-radical-scavenging activity. The ultraviolet-visible absorption of α-Toc(•) (λmax = 428 nm), which was produced by the reaction of α-tocopherol (α-TocH) with ArO(•), disappeared under the coexistence of CAs due to the α-TocH-regeneration reaction. The results suggest that the CAs may contribute to the protection from oxidative damage in nervous systems, by scavenging free radicals (such as lipid peroxyl radical) and regenerating α-TocH from the α-Toc(•) radical.