The objective of this study is to present a promising route to design a series of new poly(vinyl chloride) (PVC) films cross-linked with polyetheramine (PEA), namely jeffamine, by combining copper (I)-catalyzed azide-alkyne cycloaddition “click” reaction (CuAAC) and aza-Michael addition (PVC-Jeffs). In the first step, the clickable azido‐functional PVC is prepared easily by displacement reaction between chlorine groups and sodium azide (PVC-N3) and then reacted with propargyl acrylate by CuAAC (PVC-acr). The second step is aza-Michael addition of PVC-acr and Jeffamine to achieve the desired PVC-Jeffs. Transparent and uniform films are prepared by casting from dichloromethane solvent. The effect of loading ratio by weight (PVC/Jeffamine (w/w) = 9:1; 8:2 and 7:3) on the thermal properties of final PVC-Jeffs is systematically explored. The chemical structure of PVC-Jeffs and their intermediates is characterized by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (1H-NMR) spectroscopies, whereas thermal characteristics of the samples are investigated by thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses. The higher Jeffamine loaded PVC-Jeff exhibit enhanced thermostability and glass transition temperature with the T g of 69.9 °C. Hence, this kind of strategy to achieve the PVC based films with good characteristics is expected to be applied in the preparation of biomedical materials.