Hyperbranched Topological Design Enables Catalyst‐Free Recyclability and Exceptional Toughness in Fully Bio‐Based Epoxy Networks

ABSTRACT The fundamental paradox between robust mechanical performance and sustainable recyclability remains a critical challenge for thermosetting polymers and emerging covalent adaptable networks. Herein, a paradigm for fully bio‐based, hyperbranched dynamic epoxy networks (FGP) is presented, utilizing a rationally designed architecture to achieve an unprecedented balance of strength, toughness, and catalyst‐free recyclability. Driven by the synergistic effects of hyperbranched topology and ordered microphase separation, the resulting FGP exhibits exceptional mechanical performance, delivering a tensile strength of 69.7 MPa and a remarkable toughness of 27.3 MJ/m 3 . Crucially, the abundant terminal hydroxyl groups inherent to the hyperbranched skeleton trigger an efficient neighboring group participation effect, facilitating rapid transesterification without external catalysts and endowing the material with excellent self‐healing and shape‐memory capabilities. Furthermore, a comprehensive dual‐strategy lifecycle is established: FGP waste can either be fully depolymerized in an eco‐friendly ethanol solution for loss‐less closed‐loop recycling, or mildly degraded for direct upcycling into high‐value polyurethane foams via in situ foaming. This architectural design strategy profoundly bridges the gap between high‐performance structural requirements and end‐of‐life circularity, offering a versatile platform for next‐generation sustainable materials.