Graphene nanoplatelets (GNP) were exfoliated using a nondestructive chemical reduction method and subsequently decorated with polymers using two different approaches: grafting from and grafting to. Poly(methyl methacrylate) (PMMA) with varying molecular weights was covalently attached to the GNP layers using both methods. The grafting ratios were higher (44.6% to 126.5%) for the grafting from approach compared to the grafting to approach (12.6% to 20.3%). The products were characterized using thermogravimetric analysis–mass spectrometry (TGA-MS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The grafting from products showed an increase in the grafting ratio and dispersibility in acetone with increasing monomer supply; on the other hand, due to steric effects, the grafting to products showed lower absolute grafting ratios and a decreasing trend with increasing polymer molecular weight. The excellent dispersibility of the grafting from functionalized graphene, 900 μg/mL in acetone, indicates an increased compatibility with the solvent and the potential to increase graphene reinforcement performance in nanocomposite applications.