A labile carbon-halogen bond in alkyl halides is used as the radical source in atom transfer radical polymerization (ATRP). This method prepares graft polymers via the graft-from approach with multifunctional polymers. In this study, poly(vinyl chloride) (PVC) was used to grow diverse methacrylates. The C-Cl bond's limited thermal stability in PVC contributes to its low recycling rate, despite being the third most produced polymer globally. Waste soft PVC (i.e., tarpaulin) was treated with a solvent to isolate it, followed by filtration and precipitation. Characterization confirmed the feasibility of this recycling process. Graft polymerizations via supplemental activator and reducing agent ATRP (SARA ATRP) produced polymers with varied thermal properties depending on the (meth)acrylates used. PVC grafted with PMMA showed enhanced thermal properties and stability compared to PVC/PMMA blend. This study offers methods for recycling and upcycling thermally unstable PVC, promoting its sustainable use.