2D nanostructured fullerene (C₆₀) nanosheets (NSs) with a strong electron-withdrawing ability are employed as a hybridization matrix for improving the electrode performance of an inorganic solid. The electrostatically-driven self-assembly of anionic C₆₀ NSs with cationic Ni–Fe-layered double hydroxide (LDH) NSs yields a strongly-coupled nanohybrid of C₆₀–LDH. The hybridization between fullerene and Ni–Fe-LDH NSs leads not only to the formation of a mesoporous stacking structure but also to the occurrence of strong interfacial electron transfer from Ni–Fe-LDH to C₆₀. The obtained C₆₀–Ni–Fe-LDH nanohybrids deliver much greater specific capacitances with better rate characteristics than the graphene–Ni–Fe-LDH nanohybrid and the pristine Ni–Fe-LDH, highlighting the superior role of fullerene as a hybridization matrix over graphene in improving the supercapacitor electrode performance of the LDH material. Such remarkable advantages of fullerene incorporated are attributable to the increase of porosity, the significant contribution of the redox process of fullerene, the improvement of charge transfer kinetics, and the enhancement of surface electrophilicity due to an electronic coupling with electron-withdrawing fullerene. The present study underscores that hybridization with fullerene provides an effective way of exploring a new family of high-performance electrochemistry-related functional nanohybrids.