The compatibility of graphene or graphene oxide with its dispersion medium (polymer) plays a critical role in the formation nanocomposite materials with significant property improvements. Environmentally friendly miniemulsion polymerization, which allows a formation of nanoencapsulation in an aqueous phase and high molecular weight polymer/composite production is one promising method. In this study, we screened a series of amphiphilic modifiers and found that the quaternary ammonium (ar-vinyl benzyl) trimethyl ammonium chloride (VBTAC) pending carbon double bonds could effectively modify the graphene oxide (GO) to be compatible with the organophilic monomer. After that, free radical miniemulsion polymerization could successfully synthesize stable latex of exfoliated poly (methyl methacrylate) (PMMA)/ GO nanocomposite. The final latex had an extended storage life and a relatively uniform particle size distribution. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) analysis of this latex and its films indicated successful encapsulation of exfoliated nano-dimensional graphene oxide inside a polymer matrix.