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Using thermal expansion tests, the thermal strain evolution is shown to depend on the temperature-changing rate, which reveals the nonequilibrium states with rate-dependent structural relaxation. The influences of structural relaxation on the stress relaxation behaviors are examined in both uniaxial tension and compression modes. Assisted by a theoretical model, the study reveals how to tune the material and thermal-temporal conditions to promote the contribution of BERs during the reprocessing of vitrimers.We describe here a supramolec