The development of electrocatalysts with high activity is essential to convbar glycerol into value-added chemicals through electrocatalytic oxidation. Nano-sized metals with prickly structures are expected to possess high electrocatalytic activity due to the strong electric field at the sharp tips. We propose a facile approach to prepare Au nanoparticles with prickly structure by galvanic displacement in this work. The reaction between Au3+ and Ni generates in situ highly dispersed Au nanoparticles with prickly structures on the Ni foam. Owing to appropriate prickly structure, the Au nanoparticles prepared at 25∘C for 30 s exhibited the best electrocatalytic performance. Finite element simulation method simulations show that the high-density of positive charge at the tips forms strong electric field, which enriches OH− ions and promotes glycerol oxidation, thus exhibiting excellent electrocatalytic activity. This study will guide further design/development of electrocatalytic nanostructured Au particles and provide an effective route to electrocatalytically oxidize glycerol.