Improving the electrocatalytic activity of Pt-based catalysts is of great importance for the development of heterogeneous catalysis, fuel cells, and analytical sensors. Herein, we achieve significant enhancement of the catalytic activity of Pt–Pd bimetallic materials towards glucose electrooxidation by introducing porous architectures with three-dimensional dendritic microstructures, which were fabricated in situ on desired substrates through electrochemically reducing precursors along with periodic bubbling caused by the intermittent liberation of hydrogen. The synthesized Pt–Pd materials were characterized by SEM, nitrogen adsorption/desorption, energy dispersive spectroscopy, XRD, inductively coupled plasma optical emission spectrometry, and electrochemical techniques. Encouragingly, an extra-large active surface area of up to 80.8 m2 g−1 was obtained for the porous Pt–Pd nanostructures, almost 3.8 times that of the Pt–Pd alloys prepared by standard electrodeposition techniques. As a result, the synthesized Pt–Pd with porous frameworks exhibited remarkably improved electrocatalytic properties for glucose oxidation in neutral media, with 1.5 times the mass activity compared to the conventional Pt–Pd structure. In addition, the porous Pt–Pd catalysts could be reused at least 100 times in the presence of chloride ions, with negligible loss of activity.