The polycaprolactone (PCL)/starch blends were prepared by using the starch-g-PCL (SGCL) graft copolymers as compatibilizers, and their mechanical properties were correlated with the compatibilizing effect of the SGCL copolymers having various molecular structures. The modulus and strength of the PCL/starch blend were decreased, whereas the percent elongation and the toughness were increased remarkably with the addition of SGCL having appropriate graft structure. These property changes were analyzed in terms of the PCL crystallinity and the interfacial adhesion between the PCL matrix and starch dispersion phases, which were dominated by the compatibilizing effects of the SGCL copolymers.