Tea catechins, the most important compounds in tea polyphenols, can efficiently scavenge superoxide anion free-radical ($O_2$.), hydroxyl radical. (.OH) The mechanism of scavenging active oxygen free radicals was investigated by ESR spin trapping technique and Chemiluminescence. Results showed that various tea catechins constitute an antioxidant cycle in accordance with the decreasing order of the first reductive potential, and produce the effect of cooperative strength each other. Esterificated catechins could scavenge active oxygen free radicals more effectively than the non-esterificated ones. When.OH and $O_2$.- were scavenged by (-)-epigallocatechin gallate [(-)- EGCG], the stoichiometric factors were 6, and the rate constants of scavenging reaction reached $7.71{ imes}10^6$ and $3.52{ imes}10^{11}$ L $mmol^{-1}s^{-1}$, respectively. In the mean time, tea catechins could scavenge superoxide anion fiee radical ($O_2$-.) and hydroxyl radical (.OH) in a dose dependent manner. But at higher concentration or pH value, tea catechins can induce the prooxidant.