Using glycerol and fatty acid with different structures (octoic acid, 2-ethylhexic acid, pentic acid and 2-methylbutyric acid) as raw materials, four glyceride-derived fatty acid esters with different structures were prepared by direct esterification method, and were applied as plasticizers for PVC. The structure and purity of the plasticizers were analyzed by FTIR and 1HNMR. The PVC films plasticized by the four plasticizers were studied and compared with the PVC film plasticized by bis(2-ethylhexyl) phthalate (DEHP). The results showed that, compared with the PVC film plasticized by DEHP, the percentage of breaking elongation of glycerol trivalerate was increased by 151% in the plastic PVC film, the initial degradation temperature of the glycerin tricaprylate plasticized PVC film was 12.3 ℃ higher, the extraction resistance of glyceryl tri(2-methylbutyl) ester plasticized PVC film was better, indicating the potential to replace DEHP. Furthermore, the analysis of the relationship between the structure and performance of the plasticizers found that the PVC plasticized by plasticizers with more branches had better compatibility and extraction resistance, but the thermal stability and volatility resistance were weaker.