Blends of the modified polycaprolactone (PCL) and the gelatinized starch with glycerin were prepared. The modified PCL, PCL-g-glycidyl methacrylate (GPCL), was synthesized by melt reaction of PCL and glycidyl methacrylate (GMA) in the presence of benzoyl peroxide (BPO) in a Brabender mixer. The size of the dispersed starch in the GPCL matrix was found to be smaller than that in the PCL matrix. As the relative content of the GMA groups in the GPCL increases, the elongation at break of the blend showed the highest value at a grafted GMA content of 4.2 wt %. With the increase of the glycerin content in the starch, an abrupt change of the mechanical properties of the blend were observed between 40 and 50 wt % glycerin content based on the starch weight.