Poly(vinyl chloride) (PVC) is one of the most widely applied plastics in the world, with inherent mechanical brittleness and inflexibility in room temperature. With the growing concern for health and safety, especially in some fields (children's toys, food packaging, medical supplies) that require high‐safety plastics, there is an urgent need to develop phthalate‐free high‐performance green PVC products. Herein, by blending novel green oligomeric lactate plasticizers 1, 4‐cyclohexane dimethanol oligomeric lactate‐levulinate (CDOL‐L) and 1,4‐cyclohexane dimethanol oligomeric lactate‐levulinic acid ketal ester (CDOL‐LKE), highly stretchable and highly stable PVC‐based plastics were prepared successfully. CDOL‐L and CDOL‐LKE were synthesized by a green route of esterification and ketalization using biomass as the main raw material, and their structures were jointly confirmed by Fourier transform infrared spectroscopy, 1H NMR and TOF‐MS. Through performance testing, CDOL‐L or CDOL‐LKE plasticized PVC material were determined to have triple high stability (thermal, mechanical and migration stability) superior to DOP, DOTP and ATBC plasticized PVC. The PVC plasticized by CDOL‐L exhibited break at elongation as high as 833.0% at 50 phr addition and 877.1% at 60 phr addition. Moreover, PVC plasticized by 50 phr CDOL‐LKE exhibited relatively better thermal stability (Ti,CDOL‐LKE = 271.4°C) for the special ketal structure on the plasticizer. In conclusion, CDOL‐L and CDOL‐LKE showed potential to substitute traditional plasticizers and pointed a new direction for the preparation of high‐performance PVC‐based plastics.