Polycaprolactone-g-glycidyl methacrylate (PCL-g-GMA), a reactive interfacial agent for PCL-starch blends, is synthesized using supercritical carbon dioxide (scCO(2)) as reaction medium and relatively high molecular weight PCL (M-w = 50,000). Higher GMA and radical initiator intakes lead to higher functionalization degrees (FD) for PCL-g-GMA samples. A mathematical model is developed to describe the correlation between monomer and initiator intake and FD values. The model shows an excellent R-2-value (0.978), which implies a good fit of the experimental data. Comparison of this model with a similar one for the reaction in the melt clearly indicates a better reaction efficiency in scCO(2). Furthermore, GPC results show that less degradation occurred for samples made in scCO(2). Finally, the use of the PCL-g-GMA made in scCO(2) (as interfacial agent) in ternary blend of PCL/starch/PCL-g-GMA results in better mechanical properties with respect to those obtained by using the same graft-copolymer as prepared in the melt.