A polymerization between 1,4-diaminobenzene (PPD) and acrylic acid catalyzed by Horseradish Perodxidase (HRP) in an water buffer will be described in this article. The effects of the concentration of H2O2, the ratio of the acrylic acid to PPD, the pH of the buffer, and the reaction time of polymerization were investigated. Compared with conventional methods, the synthesis is simple and the conditions are mild. The conductivity, UV-vis spectra, FT-IR spectra, X-ray photoelectron spectroscopy (XPS), and the thermo-gravimetric analysis (TGA) of the resulting polymer were investigated also. The results show that the synthesized polymer (PAnI) is a self-doped poly(1,4-diaminobenzene-acrylic acid) with 1,4-disubstituted aromatic ring, and a higher electro-activity, water-solubility, its decomposition temperature is 498.8 °C.