The thermal degradation behavior of the biocomposite with thermoplastic starch (TPS), poly(e-caprolactone) (PCL) and bleached sisal fibers were investigated by thermogravimetry analysis (TG/DTG) under synthetic air atmosphere, differential scanning calorimetry, and their crystal structure by X-ray diffraction. Applying the non-isothermal Ozawa method, the TG/DTG curves average activation energy could be obtained for thermal degradation of the biocomposites with 5, 10, and 20 % of bleached sisal fibers. The apparent activation energy values for the biocomposites decreased when compared with the TPS/PCL blend, requiring lower energy to recycle this material. However, continuous addition of sisal fibers increased the activation energy of composites.