Palladium (Pd) nanoparticles (NPs) prepared by gas phase cluster deposition demonstrated excellent electrocatalytic activity. Herein, a series of Pd NPs modified freestanding electrodes with a super clean surface and easy repeating process for methanol oxidation reaction is reported. Pd NPs with different coverage were deposited on Ni foams and three-dimensional graphene-Ni foams, respectively. Owning to the special three-dimensional structure of Ni foam, the Pd NPs-Ni foam composite exhibited remarkable activity and unusually long-term stability for methanol electro-oxidation. The introduced three-dimensional graphene prepared by conventional chemical vapour deposition improved the electrocatalytic performance. The results can be attributed to the Pd NPs with high electrochemical activity and unique properties for three-dimensional supports. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.