Polyphenols containing Schiff base pendent groups, poly(4-[benzylidene-amino]-phenol) (PBP), and poly(4-[(anthracen-9-ylmethylene)-amino]-phenol) (PAP) have been synthesized through the combination of Schiff base reaction and enzymatic polymerization using horseradish peroxidase (HRP) as catalyst. The polymers were characterized by GPC, FTIR, H-1 NMR, and UV spectroscopy. It shows that PBP and PAP are composed of polyphenol main chains bearing Schiff base pendent side groups. The PBP exhibits better solubility than PAP in some common solvents. The PAP has a large red-shift of 86 nm compared with polyphenols, indicating the Schiff base pendent groups remarkably increase the conjugation lengths of polyphenols.