Processing polyvinyl chloride (PVC) artificial material requires plasticizer that softens the PVC coating. Currently, utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester (EFAME) bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens. However, commercial EFAMEs, even with the highest epoxy value (ca. 5.5–5.8%) so far, still suffer from fast leaching from the PVC matrix, burdening the environment and shortening lifespan of the artificial material. Here, we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester. Despite a low epoxy value (3.0%), the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value (5.8%). Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance, the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates, thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.Epoxidized methyl ricinoleate bio-plasticizer with a pendant acetate ester for PVC artificial leather: Circumventing existing limit on achievable migration resistance