As a proof of concept, new macromolecular architectures based on AMS-maleimide and PBAT oligomers were first successfully additions in a multistep approach and then fully characterized with different techniques such as complementary NMR and thermal analysis. The thiol-Michael addition between these synthesized chemical architectures has been shown. This study clearly shows the high potential of these strategies based on a fast click reaction. These compounds could be used as additives in incompatible blends and multilayers, acting at the interface between layers and/or in the core of these renewable and multiphase systems to improve their properties and to fulfill the requirements for a large range of short-term and demanding applications such as biodegradable and biobased packaging or agriculture. The very high reaction rate of a thiol-Michael addition particularly shown in a model based on modified PBAT oligomers and the precise chemical structure of the thiol-Michael adducts were shown by 1 H NMR. Thus, the reported thiol-Michael additions are promising for the fast development of macromolecular networks during processing steps. As a first perspective, the effect of this architecture must be evaluated with more practical and applied studies in connection with some targeted applications, such as the degradation properties . Practically, TPS/PBAT blends or multilayers could be rapidly and easily compatibilized using thiol-Michael addition, with an adequate catalyst, such as phosphatebuffered saline , which could be added into the thermoplastic starch formulations. The morphologies and physical, mechanical properties of these multiphase systems could be evaluated and compared to their non-compatibilized counterparts to fully assess the performance of these new architectures as additives. In specific conditions, the reversibility of thiol-Michael addition has been recently reported in the context of the development of CANs 21 .