Poly (lactic acid) (PLA) is the most widely available commercial bioplastic that is used in various medical and packaging applications and three-dimensional filaments. However, because neat PLA is brittle, it conventionally has been blended with ductile polymers and plasticizers. In this study, PLA was blended with the high-ductility biopolymer poly (butylene-sebacate–co–terephthalate) (PBSeT), and hexamethylene diisocyanate (HDI) was applied as a crosslinking compatibilizer to increase the miscibility between the two polymers. PLA (80%) and PBSeT (20%) were combined with various HDI contents in the range 0.1–1.0 parts-per-hundred rubber (phr) to prepare blends, and the resulting physical, thermal, and hydrolysis properties were analyzed. Fourier-transform infrared analysis confirmed that –NH–C=OO− bonds had formed between the HDI and the other polymers and that the chemical bonding had influenced the thermal behavior. All the HDI-treated specimens showed tensile strengths and elongations higher than those of the control. In particular, the 0.3-phr-HDI specimen showed the highest elongation (exceeding 150%) and tensile strength. In addition, all the specimens were hydrolyzed under alkaline conditions, and all the HDI-treated specimens degraded faster than the neat PLA one.