The main objective of this study is to develop an efficient strategy to obtain performing biodegradable and biobased multiphase systems for a large range of potential short-term applications, based on starch and a potential fully biobased polyester. A specific strategy based on thiol-Michael addition has been developed in this context (Figure ), as a proof of concept. This article reports the different steps to obtain PBAT oligomers with thiolated chain ends (oligoPBAT-dithiol) and the synthesis of the AMS with maleimide groups (AMS-maleimide). These different modified polymers were analyzed and largely characterized by various spectroscopies and thermal analysis. Then, the oligoPBAT-dithiol was reacted with the synthesized AMS-maleimide, with base-catalyzed thiol-Michael addition, to yield novel macromolecular architectures combining polysaccharides and PBAT in the context of more sustainable materials. Since such systems are insoluble and to estimate the kinetic of such a reaction by NMR, an equivalent system obtained by thiol-Michael addition has been also synthesized. A thiol-Michael addition between PBAT derivatives was then performed to obtain a soluble adduct as a model to evaluate the evolution of such a reaction.