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Introducing dynamic covalent bonding into thermoset polymers has received considerable attention because they can repair or recover when damaged, thereby minimizing waste and extending the service life of thermoset polymers. However, most of the yielded dynamic covalent bonds require an extra catalyst, high temperature and high-pressure conditions to trigger their self-healing properties. Herein, we report on a catalyst-free bis-dynamic covalent polymer network containing vinylogous urethane and disulfide bonds. It is revealed that the introduction of disulfide bonds significantly reduces the activation energy (reduced from 94 kJ/mol to 51 kJ/mol) of the polymer system for exchanging and promotes the self-healing efficiency (with a high efficiency of 86.92% after being heated at 100 °C for 20 h) of the material. More importantly, the mechanical properties of the healed materials are comparable to those of the initial ones due to the special bis-dynamic covalent polymer network. These results suggest that the bis-dynamic covalent polymer network made of disulfide and inter-vinyl ester bonds opens a new strategy for developing high-performance vitrimer polymers. [ABSTRACT FROM AUTHOR]