Citric acid is a widely distributed bio-based monomer, and its polyfunctionality makes its derivatives a potential choice as cross-linkers for thermosets. The utilization of bio-based precursors to prepare polymers is very beneficial for environmental protection and sustainable development. However, thermosets usually lack reprocessability and recyclability due to their permanent chemical cross-linking. To achieve sustainable recycling, the design and modification of citric acid as a precursor for vitrimers is a promising strategy. In this work, we synthesized a new cross-linker that incorporated acetoacetate groups onto citric acid and performed the synthesis and evaluation of citric-acid-based vitrimers. A series of bio-based vitrimers with different dynamic bond contents was prepared by adjusting the ratio of the reactants, and their properties were characterized. The process adopted melt polymerization without additional catalyst, which was green and environmentally friendly and avoided the problem of catalyst escape or decomposition during reprocessing. The incorporation of the amide segment enhanced the mechanical properties and the thermal stability, whereas vinyl urethane bonds provided reprocessability, degradability, and self-healing capabilities. At the same time, it was physically and chemically recycled and showed excellent stability in terms of its chemical structure and physical properties. Chemical recycling through acid-catalyzed degradation also provides a route for monomer recovery.