Constructing an appealing architecture is of great significance to improving the electrocatalytic activity and stability of Pt-based nanocatalysts. In this work, we successfully synthesized porous Pd@PdPt core/shell nanocrystals via a facile one-pot method, which possess several architectural and compositional advantages, involving porous outer, ultrathin branches, an open mesoporous skeleton, a core/shell structure, and an alloyed composition. These morphological features and the synergistic effect between different components in the alloy endow the Pd@PdPt nanostructures with abundant active sites, effective mass transfer, strain in the particle, and the electronic coupling effect. The Pd@PdPt nanoalloy therefore exhibits excellent electrocatalytic performances in alcohol oxidation reactions. Impressively, the Pd5Pt4 nanocubes exhibit a higher mass/specific activity of 3.225 A mgPt+Pd–1/34.49 A m–2 for the ethanol oxidation reaction, which is even 4.00-/2.39-fold as high as that of commercial Pt/C. Moreover, the Pd5Pt4 nanocubes also show a superior mass activity of 2.824 A mgPt+Pd–1/37.66 A m–2 toward the methanol oxidation reaction, which is up to 4.20/2.40 times that of the commercial Pt/C. The Pd@PdPt also has enhanced electrocatalytic stability. More importantly, the porous Pt5Pd4 nanocubes still demonstrate superior electrocatalytic activities of 0.259, 1.19, 2.65, and 2.76 A mgPt+Pd–1 for the oxidation of glucose, isopropyl alcohol, glycerol, and ethylene glycol, respectively. We therefore believe that these universal electrocatalysts have the potential to promote practical applications in fuel cells.