Synthesis of poly(vinyl chloride–g–ethylene glycol) [poly(VC–g–EG)] graft copolymers was carried out by me- ans of “click” chemistry of propargyl polyethylene glycol (propargyl PEG) and terminally azide polyvinyl chloride (PVC–N3). Primarily propargyl PEG was synthesized by the reaction of PEGs (3000 Da, 2000 Da, 1500 Da, 1000 Da, 600 Da, and 400 Da) with propargyl chloride. PVC–N3 was obtained by reaction of purified PVC and sodium azide. By using PVC–N3 and propargyl PEG, poly (VC–g–EG) graft copolymers were synthesized. The primary parameters such as concentration, and time that influenced the reactions were assessed. The charac- terization of products was accomplished by using multi instruments and methods such as nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, elemental analysis, and fractional precipitation [non-solvent (petroleum ether, mL)/solvent (THF, mL)] techniques.