A bio-based plasticizers, acetyl-oleate triethylene glycol (AOT), was successfully synthesized by using oleic acid as a raw material through esterification, epoxidation, and acetylation. Its structure was analyzed by Fourier transform infrared spectroscopy and 1 H nuclear magnetic resonance. The plasticizing performances of this plasticizer was compared with those of two commercial ones: dioctyl terephthalate (DOTP) and dioctyl adipate (DOA). This was done by blending these plasticizers with PVC, respectively. Thermal gravimetric analysis results showed that the 5% weight loss temperature of PVC with AOT was 53 C higher than that of DOA and 36 C higher than that of DOTP. The tensile results showed that the AOT plasticized PVC had excellent stretchability: its elongation at break with 50 phr AOT reached 697.7%. Furthermore, its transmittance was as high as 90%, showing better compatibility of ATO with PVC.