Au is an ideal noble metal for use as an electrocatalyst for the ethanol oxidation reaction owing to its high performance-to-cost ratio. The catalyst usually exists as nanoparticles (NPs) for high surface area-to-volume ratio. In the present work, a nontraditional physical approach has been developed to fabricate ultrasmall and homogeneous single-crystalline Au NPs by ion bombardment in a precision ion polishing system. Transmission electron microscopy characterizations show that the Au NPs produced with 5 keV Ar+ are highly strained to form twinned crystals, which accumulate a large amount of surface energy, and this was found to be an underlying reason causing strong catalysis. Electrochemistry tests reveal that in alkaline medium the C1 pathway occurs much more preferentially with the strained Au NPs than the normal Au NPs. The surface area-to-volume ratio is no longer the only factor that affects the performance; instead, surface energy might play a more important role in enhancing the catalytic activities.