A series of dipyrromethanes was synthesized by the tandem reaction of pyrrole and aldehyde in 40% alcohol solution at 50 oC using α-chymotrypsin as biocatalyst. This method have the merits of mild reaction conditions, shorter reaction time, broad substrate scope and no need of nitrogen protection. The results further expand the application of enzyme’s promiscuity and α-chymotrypsin in the organic synthesis.