Direct　methanol　fuel　cells　(DMFCs)　have　attracted　extensive　attention　due　to　clean,　efficient　characteristics　and　portable　applications.　In　this　work,　a　series　of　PdxCuy/reduced　graphene　oxide　(rGO)　catalysts　are　assembled　and　the　catalytic　performances　are　investigated　for　methanol　oxidation　reaction　(MOR)　in　alkaline　media.　The　intrinsic　surface　electronic　structures　of　the　PdxCuy/rGO　bimetallic　catalysts　are　also　studied　to　clarify　the　reaction　mechanism.　The　results　reveal　that　Pd1.2Cu0.2/rGO　exhibits　superior　catalytic　activity　(1101.58　A　gPd−1),　4.2　and　5.2　times　higher　than　those　of　the　commercial　PtRu/C　and　Pd/C　catalysts.　CO　stripping　suggests　that　the　onset　potential　for　CO　oxidation　on　the　Pd1.2Cu0.2/rGO　catalyst　is　lower　than　those　on　the　commercial　PtRu/C　and　Pd/C　catalysts,　implying　that　the　anti-CO　poisoning　ability　is　enhanced.　Combined　with　the　analysis　of　X-ray　diffraction　(XRD),　high-resolution　transmission　electron　microscopy　(HRTEM),　X-ray　photoelectron　spectroscopy　(XPS)　and　Raman,　the　enhanced　catalytic　activity　and　anti-CO　poisoning　ability　are　attributed　to　the　charge　transfer　and　lattice　compression　between　Pd　and　Cu,　which　modify　the　d-band　center　and　weaken　the　adsorption　of　CO.　Furthermore,　a　volcano　plot　is　found　between　the　MOR　activity　and　d-band　center,　indicating　that　the　excellent　MOR　activity　is　attributed　to　the　optimal　d-band　center　with　the　moderate　adsorption　strength　of　CO-like　intermediates.　©　2020　Elsevier　Ltd