Because developed neural cells are no longer regenerative and proliferative, achieving neural regenerations by using induced pluripotent stem cells (IPS cells) for nerve diseases have recently attracted much attention. Since the IPS cells’ growth and differentiation can be manipulated by different physical and chemicals cues, scaffolds combining the beneficial nanostructures and extracellular matrix may become an ideal interface to promote IPS cells’ neural differentiation. In this work, a biocompatible and multivalent polyanion, hyperbranched polyglycerol sulfate, is used to modify the graphene oxide to obtain bio-adhesive 2D nanosheets. After coating electrospinning nanofibers, the 2D nanosheets-functionalized nanofibrous scaffolds are applied to mediate the proliferation, lineage specification, and neural differentiation of IPS cells. The results suggest that the modified scaffolds can improve the adhesion and proliferation of IPS cells combined with high efficiency in maintaining their stemness. During the neural differentiation process, the scaffolds can promote neural differentiation and their maturity, meanwhile decreasing the lineage specification toward astrocyte. Overall, this study not only provides new multivalent/bio-adhesive nanofibrous scaffolds that integrate the chemical and physical cues to facilitate the targeted neural differentiation of IPS cells but also presents a novel pathway for the fabrication of carbon nanomaterials-based biocomposites in regenerative therapies.