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Bio-based vitrimers present a promising solution to the issues associated with non-renewable and non-recyclable attributes of traditional thermosetting resins, showcasing extensive potential for diverse applications. However, their broader adoption has been hindered by the requirement for catalyst inclusion during the synthesis process. In this study, a cardanol-based curing agent with poly-hydroxy and tertiary amine structures was prepared by a clean synthetic method under the theory of click chemistry. The reaction of a cardanol-based curing agent with diglycidyl ether of bisphenol A formed catalyst-free, self-healing, and recyclable bio-based vitrimers. The poly-hydroxy and tertiary amine structures in the vitrimers promoted the curing of epoxy-carboxylic acid in the cross-linked network and served as internal catalysts of dynamic transesterification. In the absence of catalysts, the vitrimers network can achieve topological network rearrangement through dynamic transesterification, exhibiting excellent reprocessing performance. Moreover, the vitrimers exhibited faster stress relaxation (1500 s at 180 °C), lower activation energy (92.29 kJ·mol−1) and the tensile strength of the recycled material reached almost 100% of the original sample. This work offers a new method for preparing cardanol-based epoxy vitrimers that be used to make coatings, hydrogels, biomaterials, adhesives, and commodity plastics in the future. [ABSTRACT FROM AUTHOR]