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Final properties of two thermoplastic corn starch matrices were improved by adding poly(ɛ-caprolactone), PCL, at 2.5, 5, and 10% w/w. One of the thermoplastic starch matrices was processed using water and glycerol as plasticizers (S_G) and the other one was plasticized with a mixture of glycerol and sodium alginate (S_GA). Blends were suitably processed by melt mixing and further injected. Films obtained by thermo-compression were flexible and easy to handle. Microstructure studies (SEM and FTIR) revealed a nice distribution of PCL within both matrices and also a good starch–PCL compatibility, attributed to the lower polyester concentration. The crystalline character of PCL was the responsible of the increment in the degree of crystallinity of starch matrices, determined by XRD. Moreover, it was demonstrated by TGA that PCL incorporation did not affect the thermal stability of these starch-based materials. In …