Although considerable progress has been achieved to create advanced polymer nanocomposites using nanocarbons including fullerene (C60) and graphene, it remains a major challenge to effectively disperse them in a polymer matrix and to fully exert their extraordinary properties. Here we report a novel approach to fabricate the C60@graphene nanocarbon hybrid (C60: ~47.9 wt%, graphene: ~35.1%) via three-step reactions. The presence of C60 on a graphene sheet surface can effectively prevent the aggregation of the latter which in turn helps the dispersion of the former in a polymer matrix during melt-processing. C60@graphene is found to be uniformly dispersed in a polypropylene (PP) matrix. Compared with pristine C60 or graphene, C60@graphene further improves the thermal stability and mechanical properties of PP. The incorporation of 2.0 wt% C60@graphene (relative to PP) can remarkably increase the initial degradation temperature by around 59 ° C and simultaneously enhance the tensile strength and Young's modulus by 67% and 76%, respectively, all of which are higher than those of corresponding PP/C60 (graphene) nanocomposites. These significant performance improvements are mainly due to the free-radical-trapping effect of C60, and the thermal barrier and reinforcing effects of graphene nanosheets as well as the effective stress load transfer. This work provides a new methodology to design multifunctional nanohybrids for creating advanced materials.