A highly efficient PdCu alloy nanocatalyst has been designed and synthesized, which exhibited excellent selectivity and activity toward ethylene glycol (EG) oxidation reaction with a low loading of electrocatalyst. The results of characterization show that the atom ratio of 1:1 (Pd:Cu) as well as the addition of polyvinyl pyrrolidone (PVP) and potassium bromide (KBr) contributed to the unique morphology of the as-prepared PdCu catalyst. Owing to the flower-like nanostructure and the synergistic effect between Pd and Cu, PdCu electrocatalyst has distinct enhancement in electrocatalytic performance whose forward peak current density is almost 3.2 and 4.3 times higher than that of pure Pd and commercial Pd/C electrocatalysts. We put forward that the prepared PdCu catalyst may have promising and alternative applications in direct EG alkaline fuel cells.