Graphene-fullerene hybrids were facilely fabricated by self-assembly of graphene oxide ( GO) and multi-substituted fulleropyrrolidines (PyrC(60)). The hybrids (GO-PyrC(60)) were applied as support materials to deposit Pd nanoparticle catalyst by a simple hydrothermal co-reduction approach. The as-prepared electrocatalysts (Pd/RGO-PyrC(60)) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. The RGO-PyrC(60) hybrid supported Pd catalyst with the optimal ratio of RGO to PyrC(60), exhibited much enhanced electrocatalytic activity and stability toward methanol oxidation reaction (MOR) compared to the RGO alone supported Pd as well as commercial Pd/C. The introduction of fulleropyrrolidine as spacer between graphene layers could increase the electrocatalytic activity and improve the long-term stability. This strategy may contribute to developing graphene-fullerene hydrids as effective support materials for advanced electrocatalysts. (C) 2018 Elsevier B.V. All rights reserved.