Biobased and biodegradable polymers market has experienced significant growth in recent times. This surge is primarily driven by heightened awareness of the great environmental impact and concern associated with conventional fossil-based and non-biodegradable polymers . With a large variety of commercially available macromolecular architectures, biobased and biodegradable polymers can be classified into three main categories with a large range of properties . In the last decades, multiphase systems, combining different biobased and biodegradable polymers, for instance, plasticized polysaccharides and biodegradable (co)polyesters, have been largely developed and patented. Such systems associate the main advantages of both biodegradable systems, such as the high oxygen barrier properties, the large availability and low cost for the polysaccharides part and high-water barrier properties, the easy processability and the flexibility for the polyesters counterpart. However, the large gap in polarity between polysaccharides and (co)polyesters results in high interfacial tensions, poor compatibility and low adhesion at the interfaces or interphases . To overcome these major issues, many compatibilization strategies have been investigated allowing the development of more or less performing multilayers and blends , such as the addition of a copolymer system comprising blocks compatible with each phase . Several macromolecular architectures have been developed and reported in this context, comprising covalent bonds between polysaccharides and polyesters by different grafting methods, such as the ring opening polymerization of cyclic esters onto the hydroxyl (OH) groups of the polysaccharides, the direct polycondensation starting on OH groups, or the radical couplings or catalyzed esterifications . Those conventional methods yielded polyester-grafted polysaccharides with different levels of efficiency. Another more recent and relevant grafting strategies are based on click chemistry, i.e. quick and quantitative reactions, performed under mild conditions and producing inoffensive and easily removable byproducts . In a previous work, a thermally reversible network based on reversible and click Diels-Alder (DA) reaction, from amylomaize starch (AMS) and PBAT was developed . This was achieved after chemical modifications of AMS and PBAT, to synthesize AMSmaleimide and PBAT-difuran, respectively, which were able to form a cross-linked network by DA reaction at 65 °C. This network was successfully un-cleaved by retro DA at higher temperatures . Considering the cleavage kinetic, thiol-Michael addition presents some strong advantages as one of the fastest click reactions. It has been successfully used to synthetize thermosets and hydrogels from biobased and biodegradable polymers, such as lignin , chitosan , or collagen , mainly for biomedical applications . Thiol-Michael addition takes place between a thiol, labelled as the Michael donor, and an activated double bond, labelled as the Michael acceptor. It is generally base-catalyzed but can also be nucleophile-catalyzed . The reaction is favored mainly by the electron deficiency of the Michael acceptor and the acidity of the Michael donor . Accordingly, maleimides are amongst the most reactive and suitable Michael acceptors and allow highly selective and efficient chemical modifications when they are incorporated into the polymer structures . In addition to fast kinetics, thiol-Michael addition is particularly convenient as it is insensitive to oxygen or water and can be performed under mild reaction conditions . The reversibility of thiol-Michael addition, enabled by an elimination reaction in some specific conditions, has been recently studied in the context of applications based on covalent adaptable networks (CANs) .