Graphene oxides (GOs), which has been extensively investigated as promising precursors for the mass production of graphene, exhibits a unique type of building block with hydrophilic oxidative debris on the edge and hydrophobic domains on the basal plane. Based on this “amphiphilic” feature, GOs can be applied as surfactants and emulsifiers in polymer blends. With the improvement of GO decoration by various functional groups, it is proposed that the GOs could be chemically tailored to be have dual or “amphiphilic” interactions with polymer pairs in order to realize the effective interfacial adhesion of immiscible blends. In this work, polystyrene (PS) grafted graphene oxide (PS-GO) was chemically designed to strengthen interfacial adhesion of immiscible blends polyamide/acrylonitrile–butadiene–styrene (PA6/ABS). It was found that in the blend composites, the PS–GO located at interface of immiscible blends PA6/ABS and enhanced the interfacial adhesion via the dual interactions with two components, in which one was the electronic stacking interaction between grafted PS on PS–GO and ABS while the other one was the interaction between polar groups on PS–GO and PA6. Finally the mechanical testing showed the elongation at break increased by nearly 400% and the impact strength increased by nearly 200% with only 0.5 wt% PS–GO, indicating the significant toughening effects of PS-GO. This work provides a new strategy to realize the interfacial enhance of immiscible blends.