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Provided are a preparation method of a highly-active tackifying chain extender without monomer residue and the use thereof; the preparation method comprises the following steps: mixing an aromatic vinyl monomer, an acrylate-based monomer and an initiator with a solvent or water, carrying out heating polymerization, and then carrying out double-screw secondary reaction granulation to prepare the tackifying chain extender without monomer residue. The epoxy functionalized chain extender of the present invention can be applied to recycled polyester structural materials, and can be applied to the repair and growth of bio-based and biodegradable plastic molecular chains with polyester structures. The present invention is simple in terms of control over the selected process and low in investment, and the product is stable in composition, simple to use and widely applicable in the fields of medical treatment, packaging, household appliances, automobiles and the like. The present invention has very broad application prospects and industrial values.