In this work, graphene oxide (GO) and poly(methyl methacrylate) (PMMA) grafted GO reduced by dopamine (rGO@PDA-g-PMMA) were employed to determine the key factor responsible for the improved mechanical properties of poly(vinyl chloride) (PVC). Dopamine was utilized to reduce GO and simultaneous coating of polydopamine (PDA) on the GO surface. rGO@PDA-g-PMMA was prepared by a combination of mussel-inspired chemistry and surface-initiated atom transfer radical polymerization techniques. The resulting derivatives were characterized by thermogravimetric analysis, Fourier transforms infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. PVC nanocomposites containing GO derivatives were prepared by solution blend and the nanocomposite films were obtained using a casting method. The mechanical properties of the nanocomposites were studied using both dynamic mechanical thermal analysis and tensile testing. The results revealed that the vital components responsible for the improved mechanical properties and thermal stability of rGO@PDA-g-PMMA/PVC nanocomposites compared to pure PVC are the interfacial interactions between the GO derivatives and the PVC matrix.