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The influences of ethylene-based elastomer (EE) and the compatibilizer agent ethylene-butyl acrylate-glycidyl methacrylate (EBAGMA) on the thermal degradation of PLA/EE blends were evaluated by the thermal degradation kinetics and thermodynamic parameters using thermogravimetry. The presence of EE and EBAGMA synergistically improved the PLA thermal stability. The temperature of 10% of mass loss (T_10%) of PLA was around 365 °C, while in the compatibilized PLA/EE blend, this property increased to 370 °C. The PLA average activation energy (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><msub><mrow><mi mathvariant="normal">E</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula>) reduced in the PLA/EE blend (from 96 kJ/mol to 78 kJ/mol), while the presence of EBAGMA in the PLA/EE blend increased the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><msub><mrow><mi mathvariant="normal">E</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula> due to a better blend compatibilization. The solid-state thermal degradation of the PLA and PLA/EE blends was classified as a D-type degradation mechanism. In general, the addition of EE increased the thermodynamic parameters when compared to PLA and the compatibilized blend due to the increase in the collision rate between the components over the thermal decomposition.