Vitrimer with covalent adaptable networks is a kind of dynamic crosslinked polymers that can be reprocessed and selfrepaired. However, the unitary functionality and poor responsiveness to external stimuli of vitrimers result in limited potentials 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 into 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 are used to investigate the molecular motion of the TER network, providing significant implications for RIM mechanism of AIE in this AIE-active vitrimer. Moreover, as a dynamic crosslinked network, TER is a promising versatile material with excellent photoluminescence, and reshaping, reprocessing as well as shape-memory properties. The AIE-active vitrimer not only represents a huge potential for further development of dynamic covalent polymers, but also extends the applications of vitrimer in different fields.