Because of their propensity to build micellar nanostructures, amphiphilic block copolymers (ABCs) are an appropriate and unique toughening agent for epoxy systems individually on their own and in grafted form. The presence of epoxiphilic and phobic ends in ABCs is responsible for the self-assembly and the micellar structure. Nanofiller-grafted ABCs can effectively enhance the toughness of epoxy via the synergistic interaction of nanofillers and the ABCs. Even though there is sound literature supporting the effect of ABCs in epoxy, the action of double hydrophilic block copolymers (DHBC) in the epoxy matrix is less handled. Hence, the grafting of nanofillers in DHBCs and their subsequent role in tuning the properties of epoxy is a new concept. Hence this paper tries to bridge the gap via studying the effect of grafted fillers based on DHBCs in epoxy matrix. As a result, the current study focuses on the synthesis of double hydrophilic graphene nanoplatelets (rGO-g-DHBC) via nitrogen oxide-mediated polymerization for epoxy toughening application. The prepared rGO-g-DHBC was effectively utilized for epoxy toughening applications, resulting in a 457% improvement in toughness without compromising its inherent tensile strength. The mechanism behind the improved toughness was elucidated with the help of a scanning electron microscope, and the thermal, and rheological characteristics were studied.