We　report　a　very　easy　and　effective　approach　for　synthesizing　unique　palladium-on-gold　supra-nanostructure　(Au@Pd-SprNS)-decorated　graphene　oxide　(GO)　nanosheets.　The　SprNSs　comprising　Au　nanorods　as　core　and　a　unique　close-packed　assembly　of　tiny　anisotropic　Pd　nanoparticles　(NPs)　as　shell　were　homogeneously　distributed　on　the　GO　surface　via　electrostatic　self-assembly.　Compared　with　the　traditional　one-pot　method　for　synthesis　of　metal　NPs　on　GO　sheets,　the　size　and　shape　of　core-shell　Au@Pd　SprNSs　can　be　finely　controlled　and　uniformly　distributed　on　the　GO　carrier.　Interestingly,　this　Au@Pd-SprNSs/GO　nanocomposite　displayed　high　electrocatalytic　activities　toward　the　oxidation　of　methanol,　ethanol,　and　formic　acid,　which　can　be　attributed　to　the　abundance　of　intrinsic　active　sites　including　high　density　of　atomic　steps,　ledges　and　kinks,　Au　Pd　heterojunctions　and　cooperative　action　of　the　two　metals　of　the　SprNSs.　Additionally,　uniform　dispersion　of　the　SprNSs　over　the　GO　nanosheets　prevent　agglomeration　between　the　SprNSs,　which　is　of　great　significance　to　enhance　the　long-term　stability　of　catalyst.　This　work　will　introduce　a　highly　efficient　Pd-based　nanoelectrocatalyst　to　be　used　in　fuel　cell　application.