Ultrathin metal nanostructures have received extensive attention in the field of electrocatalysis owing to their large surface area and high electron/mass transfer efficiency. Here, large-size Pd nanosheets-assembled nanofilms were synthesized with a facile strategy. The structural advantages endowed Pd nanofilms with outstanding electrocatalytic performance toward ethanol oxidation, including larger electrochemical active surface areas, excellent mass activity, better CO anti-poisoning ability and stability. This work may provide a novel idea for the design and synthesis of high-efficient electrocatalysts.