Electro-upgrading of low-cost alcohols such as ethylene glycol is a promising and sustainable approach for the production of value-added chemicals while substituting energy-consuming OER in water splitting. However, the sluggish kinetics and possibility of C-C dissociation make the design of selective and efficient electrocatalysts challenging. Herein, we demonstrate the synthesis of a hollowed bimetallic PtAg nanostructure through an in situ dynamic evolution method that could efficiently drive the selective electrochemical ethylene glycol oxidation reaction (EGOR). The resulting mild surficial oxidation has intrinsically improved EGOR activity, exhibiting a remarkable performance toward glycolate (selectivity up to 99.2% and faradic efficiency ∼97%) at high current density with low overpotential (355 mA·cm