Triboelectric nanogenerators are believed to be a promising solution to energy crisis by mechanical-to-electrical energy conversion through the contact electrification between constituent tribo-materials. However, most of the current tribo-materials are difficult to be repaired if damaged, and recycled for their reuse or disposal, limiting the development for reusable and sustainable energy-harvesting devices. Therefore, we explore the development of durable, repairable and recyclable triboelectric nanogenerators based on an epoxy-derived vitrimer (EV) with thermo-reversible cross-linked networks. Rather than polymerizing the EVs by adding thermoplastic components, they are generated by a solvent-free, quasi-thermoforming and scalable process. Thanks to the flowability of cross-linked networks realized by thermo-triggered hydroxyl/ester bond-exchange reactions, surface-micropatterned EV film based tribo-materials are successfully fabricated by a thermal micro-imprinting process, showing 3D shape-adaptive thermoforming ability. The EV films exhibit excellent flexibility and ductility with the smaller elastic hysteresis under external deformations, whose molecular origin is revealed to be the achievable macromolecular segment relaxation and energy dissipation of networks. The favorable mechanical robustness and recoverability endow the EV-based nanogenerators (EV-TENG) with significantly durable electricity-generating performances under repeated compressions (≥10,000 cycles) and larger mechanical loads. More importantly, by taking the triboelectric signal as a probe for network evolution, repairability and recyclability of EV-TENGs are further evaluated quantitively. Interestingly, the introduction of EVs makes the device self-repairable simply by heating treatment with a higher healing efficiency of 98%. Moreover, the device could be recycled by both physical and chemical approaches, without losing the original triboelectric performance and structural integrity. Our results demonstrate the potential applications of vitrimers derived from industrial raw materials in developing repairable, recyclable and scalable energy-harvesting electronics with prolonged lifetimes and environmental sustainability.