In this study, palm oil was the first time to convert into a novel polyester plasticizer for polyvinyl chloride (PVC). In the first stage, palm oil was converted into palm oil monoglyceride (POM) by alcoholysis with glycerol. Next, a novel palm oil monoglycerides based polyester plasticizer (POMP) was synthesized from POM and maleic anhydride through esterification and condensation reaction. The structure of POMP was characterized with FTIR, 1H NMR and GPC. Then PVC blends were prepared using POMP as a plasticizer, melting behavior, thermal property, compatibility, mechanical properties and mechanism of plasticization of PVC blends were systematically studied. Melting behavior indicated that POMP could decrease the torque and the melt viscosity of PVC blends that was conducive to process. With the content of POMP increasing from 5 g to 15 g in PVC blends, the plasticized PVC blends demonstrated better compatibility, the degradation temperature (Td) increased from 252.6°C to 257.0°C, the glass transition temperature (Tg) decreased from 55°C to 49.5°C. Plasticization was put into effect by interaction of the electron cloud between the PVC chain and POMP molecule. This study may lead to the development of new type of PVC plasticizer based on vegetable oil.