Polyguaiacol was successfully synthesized by enzyme-catalyzed polymerization in an aqueous micelle system with horseradish peroxidase (HRP) as the catalyst. As-synthesized polyguaiacol was characterized by infrared spectrometry and gel permeation chromatography, and its thermal stability was evaluated by thermogravimetric analysis. Besides, the thermal antioxidant behavior of the as-synthesized phenolic polymer as an antioxidant in polypropylene was evaluated by differential scanning calorimetry and accelerated aging test, and the apparent activation energies of thermal decomposition of polypropylene (PP) were calculated by Friedman method. Results show that the as-synthesized polyguaiacol as an antioxidant is able to significantly increase the oxidation induction time of virgin PP, and it exhibits better antioxidative performance than corresponding monomer. Moreover, polyguaiacol, the as-synthesized phenolic polymer, exhibits good resistance against aging of polypropylene.