Vitrimers with covalent adaptable networks are a class of dynamic crosslinked polymers that can be

reprocessed and self-repaired. However, their unitary functionality and poor responsiveness to external

stimuli limit the potential of vitrimers for applications as smart materials. Herein, we proposed a new

strategy by constructing an aggregation-induced emission (AIE)-active vitrimer (TER) via crosslinking

epoxy derivatives of tetraphenylethylene to form a dynamic covalent network. The activated

intramolecular rotation of AIEgen motifs with increasing temperature endows this vitrimer with thermal

responsive photoluminescence. 1H static and 1H–13C wideline separation SSNMR experiments were used

to investigate the molecular motion of the TER network, providing significant implications for the RIM

mechanism of AIE in this AIE-active vitrimer. Moreover, as a dynamic crosslinked network, TER is a

promising versatile material with excellent photoluminescence, reshaping, reprocessing and shapememory

properties. The AIE-active vitrimer not only represents a huge potential for further development

of dynamic covalent polymers, but also extends the applications of vitrimers in different fields.