A phenol copolymer poly(PHBA-co-PHSA) was synthesized by radical copolymerization of p-hydroxybenzoic acid and p-Hydroxybenzene sulfonic acid using HRP/H2O2 initiation. The effects of monomers ratio and HRP dosage on tanning properties of phenol copolymer were investigated. The structure of phenol copolymer was characterized by FTIR, NMR and GPC. The remarkable features of enzymatic radical polymerization are propagation of polymer chain by radical transfer and its molecular weight easy to control and produce conjugated system in its molecule. The results have led to the high activity of functional groups of copolymer and exhibited excellent tanning effects and benefited for dyeing and fatiliquoring of leather. The tanning results indicated that the shrink temperature (Ts) of tanned leather can reach to 78.6℃. Meanwhile the retanned leather is excellent in softness and fullness. The phenol copolymer in conjunction with chrome tannage shows better tanning results and the chrome tannage can be decreased.