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Tea is one of the most popular beverages worldwide. The major components of green tea include (−)-epicatechin (EC), (−)-epicatechin -3-O-gallate (ECG), (−)-epigallocatechin (EGC) and (−)-epigallocatechin- 3-gallate (EGCG). The typical pigments in black tea are theaflavins (TFs) and thearubigins (TRs), which are formed by oxidation of catechins during fermentation processing. Polyphenoloxidase (PPO) and peroxidase (POD) are two key enzymes in pigment formation during the process of black tea. Many studies have been conducted to reveal how PPO and POD catalyze the formation of dimers, trimer and polymers from tea catechins. However, there were few reports to summarize catalytic reaction of PPO and POD until now. The present review summarized the studies regarding the transformation of catechins to different kinds of dimers, trimers and polymers in various conditions.