The design of nanocatalysts by controlling pore size and particle characteristics is crucial to enhance the selectivity and activity of the catalysts. Thus, we have successfully demonstrated the synthesis of binary PdPb alloy nanocubes (PdPb NCs) by controlling pore size and particle characteristics. In addition, the as-obtained binary PdPb NCs exhibited superior electrocatalytic activity of 4.06 A mg–1 and 16.8 mA cm–2 toward ethylene glycol oxidation reaction and 2.22 A mg–1 and 9.2 mA cm–2 toward glycerol oxidation reaction when compared to the commercial Pd/C. These astonishing characteristics are attributed to the attractive nanocube structures as well as the large number of exposed active areas. Furthermore, the bifunctional effects originated from Pd and Pb interactions help to display high endurance with less activity decay after 500 cycles, showing a great potential in fuel cell applications.