Abstract: Traditional polymer materials were divided into thermoplastic materials and thermoset materials. Thermoplastic materials could be processed twice but not rigid enough, and thermoset materials were rigid but difficult to recycle. The glass-like polymer material was between thermoplastic material and thermosetting material, which was a kind of material with high crosslinking density network and could be processed twice. Based on the network exchange mechanism of Vitrimer, this paper focused on the development history and research progress of bio-based glass polymers. Bio-vitrimers based on different covalent bonds were introduced in detail. Generally, the conditions of dynamic transesterification reaction were relatively mild, the reaction speed was fast, and the reaction materials were extensive, while the mechanical properties and reversibility of materials were poor. The reversibility and controllability of dynamic disulfide bond exchange were better, and the reaction was not harsh to the external acid-base environment, while the reaction substrate generally had toxic behavior and pungent odor. Dynamic imine bond exchange could make the material had good mechanical properties and durability, and good biocompatibility, while the reaction conditions and raw material selection were relatively simple. The application and advantages of bio-based Vitrimer materials were reviewed. The introduction of dynamic covalent bonds made up for the shortcomings of traditional 3D printing materials, such as insufficient rigidity and single function, enhanced the comprehensive performance of carbon fiber composites, and improved the service life and self-healing efficiency of elastomer materials. Finally, the paper gived a prospect of the future development.