To effectively mitigate carbon emissions and promote sustainability in the polymer field, biological macromolecules have emerged as a prominent strategy for fabricating functional materials. Herein, tannin (TA) was used as a biological curing agent to design fully bio-based polylactic/epoxidized natural rubber thermoplastic vulcanizates (PLA/ENR TPVs) with mechanical robustness and multi-stimuli-responsive shape memory properties. A dual cross-linking network, comprising both covalent bonds and hydrogen bonds, was successfully constructed in the ENR phase. A special co-continuous morphology was concomitantly constructed in the TPVs, which promoted effective stress transfer between the PLA and ENR phases, endowing the TPVs with balanced stiffness-toughness and shape memory properties. Moreover, the photothermal effect of TA also made it respond to near-infrared light and sunlight, which achieved the non-contact multistage shape memory performance, revealing the significant potential of the TPVs in the field of actuators.