Herein, we describe the preparation of a self-catalyzed polyester vitrimer containing tertiary amino groups on the network strands that overcomes the significantly slow bond exchange often encountered in the reported systems. Starting from a polyester precursor bearing both carboxy and tertiary amino side groups, a selective reaction of the carboxyl groups with diepoxy cross-linkers affords a network that possesses hydroxy and tertiary amino groups. The tertiary amino groups on the network strands effectively work as internal catalysts for the trans-esterification bond exchange. Because of the high mobility of the incorporated internal amine catalyst, the bond exchange in the vitrimer material was much more rapid (more than 20 times) than that in reported self-catalyzed polyester vitrimers.