Abstract: As a kind of multi-copper oxidases，laccase can catalyze the polymerization of phenolic，aromatic compounds with amino groups，and some bioactive substances with the concomitant reduction of oxygen to water in a four-electron transfer process. Accordingly，researchers have paid increasing attention to the catalytic mechanisms and applications of laccases. This review provides a brief discussion about the catalytic structure and applications of laccases in organic synthesis. The characteristics of structure，redox potential and its influencing factor，and laccase-mediator system are dedicated in the structure part. The homo- and co-polymerizations，cross-coupling oxidation，and non-phenolic substrates oxidized by laccase-mediator system were emphasized in the organic synthesis category. Finally，the current research and perspective of laccase in organic synthesis are discussed.