The invention provides a method for catalyzing gamma-valerolactone to be subjected to ring-opening polymerization by utilizing a biomimetic catalyst and belongs to the field of biomass high molecular materials. According to the method, the gamma-valerolactone is used as a monomer, the biomimetic catalyst is used as a catalyst and an alcohol compound is used as an initiator, and the gamma-valerolactone is subjected to the ring-opening polymerization in a solvent to obtain poly-gamma-valerolactone; the biomimetic catalyst is one or a mixture of more of a thioureaamide type dihydrogen bond donor catalyst, an aminothiazole type dihydrogen bond donor catalyst and a phenyl phosphate type dihydrogen bond donor catalyst. Compared with a traditional catalyst, the aminothiazole type biomimetic catalyst, the thioureaamide type biomimetic catalyst and the phenyl phosphate type biomimetic catalyst have no metal and the utilization amount is small; the catalysis effect is higher under the action of a dihydrogen bond.