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Delivery systems based on amphiphilic block copolymers have shown particular relevance in the biomaterials field thanks to their diverse and modular properties, including high loading capacity, controlled release, and the ability to tune self-assembly into various nanostructures. Among these structures, supramolecular hydrogels formed from amphiphilic block copolymers are particularly investigated, despite their frequent lack of degradability. In this context, poly(amino esters) derived from N acylated-1,4-oxazepan-7-ones (OxPs) emerge as promising candidates in the development of new and degradable amphiphiles for hydrogel preparation and delivery platform formulations. Here, the synthesis of amphiphilic triblock copolymers by ring-opening copolymerization (ROCP) of OxP monomers with various pendant chains is reported. Copolymerization reactions using organocatalysts and 1,4 benzenedimethanol (DiOH) as a bifunctional initiator afforded neutral P(OxPMe) b P(OxPBn) b P(OxPMe) and cationic P(OxPNH2+) b P(OxPBn) b P(OxPNH2+) amphiphilic triblock copolymers with controlled molar masses and narrow dispersities (Đ ≤ 1.21). By tuning the reaction conditions, a panel of polymeric materials with various block lengths and compositions was synthesized. The study of their self-assembly in water revealed the formation of nanostructures, including worm-like or spherical morphologies, which were correlated to the macromolecular structure of the amphiphile. In addition, hydrogel formation using the block copolymers has demonstrated that modulation of the copolymer composition and concentration enables control over the macroscopic properties of the hydrogels. Finally, we investigated the formulation of a hydrophobic fungicide in the hydrogels and their inhibitory effect on spore proliferation, which show great promise as dispensable and biodegradable hydrogel formulations for agrochemical applications.