The lack of suitable lignin model compound limits the understanding of the characteristics of lignin, and hence hinders the efficient utilization of this kind of bioresource. A tetramer phenolic lignin model compound composed of 5-5, a-O-4 and b-5 linkages was prepared by a two-step of free radical reaction with hydrogen peroxide/horseradish peroxidase and S2O82 /Fe2+as the initiator. Compared with enzymatic process, this synthetic process gives a higher yield of 33.8% within a shorter time. HRMS and13 C NMR spectroscopy show that synthesized model compound contains phenylpropane structure linked by 5-5, a-O-4 and b-5 bonds, which can mimic some chemical characteristics of lignin. The lack of suitable lignin model compound limits the understanding of the characteristics of lignin, and hence hinders the efficient utilization of this kind of bioresource. A tetramer phenolic lignin model compound composed of 5-5, aO-4 and b-5 linkages was prepared By a two-step of free radical reaction with hydrogen peroxide / horseradish peroxidase and S2O82 / Fe2 + as the initiator. this synthetic process gives a higher yield of 33.8% within a shorter time. HRMS and 13 C NMR spectroscopy show that synthesized model compound contains phenylpropane structure linked by 5-5, aO-4 and b-5 bonds, which can mimic some chemical characteristics of lignin.