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This research focused on the development of biomaterials based on cassava starch and corn starch and on the effect of the incorporation of polycaprolactone (PCL) on the thermal and thermomechanical properties of the blends. The results indicated partial compatibility in the blends, especially with cassava starch at a content of 20 wt% as reflected by the maintenance of tensile strength and elongation. In addition, the changes in the crystal quality of PCL and the displacement of the absorption bands of the carbonyl groups of PCL in the infrared (989–1000 cm−1), attributed to the formation of hydrogen bonds between these groups and the hydroxyl groups of starches, were also associated with compatibility. It was observed that the crystallinity of PLC in the presence of cassava and corn starch was 38% and 62%, respectively; a crystallinity greater than that of PCL was related to an improved nucleation at the interface. Based on these properties, the blends are expected to be functional for the manufacture of short-term use products by conventional thermoplastic processing methods.