To obtain fully degradable and super-tough poly(lactide-co-glycolide) (PLGA) blends, biodegradable star-shaped PCL-b-PDLA plasticizers were synthesized using natural originated xylitol as initiator. These plasticizers were blended with PLGA to prepare transparent thin films. Effects of added star-shaped PCL-b-PDLA plasticizers on mechanical, morphological, and thermodynamic properties of PLGA/star-shaped PCL-b-PDLA blends were investigated. The stereocomplexation strong cross-linked network between PLLA segment and PDLA segment effectively enhanced interfacial adhesion between star-shaped PCL-b-PDLA plasticizers and PLGA matrix. With only 0.5 wt% addition of star-shaped PCL-b-PDLA (Mn = 5000 g/mol), elongation at break of the PLGA blend reached approximately 248%, without any considerable sacrifice over excellent mechanical strength and modulus of PLGA.