A simple one step synthesis of pinoresinol and its derivatives-active components of Du-Zhong (Eucommia ulmoides)-from coniferyl alcohol and p-courmaryl alcohol with higher yields was achieved by Rhus laccases (RL) catalysis in water miscible organic solvents. Biomacromolecules dehydrogenative polymers (DHP) were only synthesized by fungal laccases, not by RL. The structures and the reaction mechanism were discussed to promote the understanding of the function of laccases in the process of lignin biosynthesis.