Previous studies shown that thermoplastic blends of corn starch with some biodegradable synthetic polymers (poly(epsilon-caprolactone), cellulose acetate, poly(lactic acid) and ethylene-vinyl alcohol copolymer) have good potential to be used in a series of biomedical applications. In this work the thermal behavior of these structurally complex materials is investigated by differential scanning calorimetry (DSC) and by thermogravimetric analysis (TGA). In addition, Fourier-transform infrared (FTIR) spectroscopy was used to investigate the chemical interactions between the different components. The endothermic gelatinization process (or water evaporation) observed by DSC in starch is also observed in the blends. Special attention was paid to the structural relaxation that can occur in the blends with poly(lactic acid) at body temperature that may change the physical properties of the material during its application as a biomaterial. At least three degradation mechanisms were identified in the blends by means of using TGA, being assigned to the mass loss due to the plasticizer leaching, and to the degradation of the starch and the synthetic polymer fractions. The non-isothermal kinetics of the decomposition processes was analyzed using two different integral methods. The analysis included the calculation of the activation energy of the correspondent reactions.