The development of efficient anode nanocatalysts with high performance for direct ethylene glycol fuel cells is highly desirable and still difficult due to the sluggish kinetics at the anode. For that reason, it is necessary to engineer cost-effective Pd-based catalysts with fascinating structure and superior activity. Inspired by this, we shed light on a facile self-template one-pot approach to synthesize sub-24 nm PdAg hollow nanodendrites with tunable compositions. More importantly, owing to the exquisite hollow nanostructure and electronic effect, as well as synergistic role, the as-prepared unique binary PdAg nanocatalysts show outstanding mass activity of 4168.8 mA mg(pd)(-1) for ethylene glycol oxidation reaction under the alkaline medium, 3.8-fold enhancements than that of commercial Pd/C catalysts. Remarkably, based on this facile synthesis method and superior electrocatalytic performance of as-prepared catalysts, we believe that our efforts will open a new way to promote the commercialization of fuel cells to some extent.