<p>In this research, poly(vinyl chloride)-graft-polycaprolactone (PVC-<i>g</i>-PCL) polymeric plasticizers were synthesized via the sequential atom transfer radical polymerization (ATRP) and ring-opening polymerization. First, utilizing the grafting-from technique, poly(hydroxyethyl acrylate) (PHEA) was grafted on the backbone of PVC by means of ATRP polymerization. In the second step, hydroxyl groups of the PHEA acted as initiating sites for grafting of the polycaprolactone (PCL) to the backbone of PVC to obtain PVC-<i>g</i>-(PHEA-<i>g</i>-PCL) graft copolymers. Hydrogen nuclear magnetic resonance and Fourier transform infrared spectroscopy analyses confirmed the successful synthesis of copolymers in both steps. Differential scanning Calorimetry analyses showed that the glass transition temperature of PVC can be decreased to subzero temperatures by increasing PCL content. At the same time, further analyses confirmed the nonmigratory behavior of newly synthesized copolymers in the PVC matrix. The tensile properties of the PVC/PVC-<i>g</i>-(PHEA-<i>g</i>-PCL) films showed comparable ductility with the PVC films plasticized with a dioctyl phthalate conventional plasticizer. As phthalate-based plasticizers are easily extracted from the PVC matrix, the PVC-<i>g</i>-(PHEA-<i>g</i>-PCL) copolymers synthesized in this work can be used as permanent plasticizers for PVC.</p> Graphical abstract <p></p>