Display omitted •VAn-P breaks the record of plasticity of flame-retardant plasticizers.•The VAn-P addresses the issue with traditional flame-retardant solutions.•Vanillate plasticizer VAn-P has a multi-functional gain on PVC.•Effects of chain length on vanillate plasticizer is novelly studied. The current market for poly(vinyl chloride) (PVC) plasticizers is dominated by flammable petroleum-based compounds, accounting for over 80 % of the total share. Due to their high flammability, the search for novel approaches to enhance the fire resistance of flexible PVC has gained urgency. However, traditional flame-retardant schemes suffer from shortcomings such as poor compatibility, inferior long-term performance, and weak mechanical properties. Herein, we synthesized a novel biobased flame-retardant plasticizer (VAn-P) using vanillic acid as a skeleton. This plasticizer exhibits remarkable properties, including a substantially lower glass transition temperature compared to unplasticized PVC. The binding energy between VAn-P and PVC is calculated to be –33.30 kcal/mole, indicating a strong interaction. Furthermore, the maximum elongation at break of VAn-P plasticized PVC is 16 times higher than that of unmodified PVC. All PVC samples plasticized with VAn-P achieved a UL-94 VTM-0 rating. TGA-FTIR analysis revealed that the flame-retarding mechanism of VAn-P involves solid-phase action, significantly delaying the dehydrochlorination process of PVC. Moreover, VAn-P exhibits superior migration resistance compared to dioctyl phthalate (DOP). We also investigated the effects of alkyl chain lengths in VAn-P on various properties of PVC blends, including thermal stability, flame retardancy, mechanical properties, and optical performance. The toxicity of vanillic acid-based flame-retardant plasticizer has undergone an initial assessment. Overall, this green plasticizer is expected to endow polymers with high plasticizing performance and flame retardancy, providing a novel and sustainable approach for the synthesis of functional plasticizers.