Two different biodegradable polyesters [polycaprolactone (PCL) and poly(3-hydroxybutyrate-co-valerate) (PHBV)] were blended with a maize Starch that had high amylose content through the use different reactive approaches. The compatibilization of both systems was obtained. PCL/starch composites were obtained by the addition of a third reactive component that was able to act as a coupling agent, and the reactive interface of PHBV/starch composites was improved during blending with an organic peroxide. Thermal, morphological, and mechanical characterization showed that the compatibilized composite materials had better final proprieties than neat materials or composites prepared without compatibilization. Finally, the degradation of all prepared materials by a compost simulation test was investigated.