A method for preparing a highly elastic biodegradable three-dimensional structure includes (a) mixing poly(lactide-co-ε-caprolactone) (PLCL) with at least one biocompatible heat stabilizer that is biocompatible with the PLCL, that is a heat stabilizer for the PLCL, and that is selected from the group consisting of α-tocopherol, barium-zinc, calcium-zinc, vitamin B, and combinations thereof to provide a solvent-free mixture; and (b) carrying out three-dimensional printing with the solvent-free mixture by heating the mixture at 150-250° C. for 5-20 minutes to provide a heated mixture; and ejecting the heated mixture through a nozzle. The three-dimensional structure maintains mechanical properties even after three-dimensional printing, by adding a biocompatible heat stabilizer to poly(L-lactide-co-ε-caprolactone). The three-dimensional structure is useful as a scaffold for tissue engineering.