The non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen is an industrially relevant chemical conversion. Although Cu-based catalysts show high reactivity toward oxidative ethanol dehydrogenation, the flat Cu(111) surface is rather inactive for ethanol dehydrogenation in the absence of water, surface oxygen or defects. Herein we show, using experimental and theoretical studies of model systems, that adding 1% Pt into the surface of Cu(111) to form dilute Pt-Cu single atom alloys (SAAs) increases the activity of Cu(111) for ethanol dehydrogenation sixfold. The mechanism of ethanol dehydrogenation was investigated at the molecular level using scanning tunneling microscopy, temperature programmed experiments and density functional theory calculations. Our results demonstrate that Pt-Cu SAAs are much more active than Cu(111) for converting ethanol to acetaldehyde and hydrogen in the absence of surface oxygen and water. Specifically, the O-H bond of ethanol is activated at Pt sites below 160 K, followed by ethoxy spillover to Cu sites which results in a significant increase of the ethoxy intermediate yield. The C-H bond of ethoxy is then activated at 310 K, and the final product, acetaldehyde, desorbs from Cu(111) in a reaction rate limited process. Finally, we show that the Cu model surfaces exhibit stability with respect to poisoning as well as 100% selectivity in the alcohol dehydrogenation to acetaldehyde and hydrogen.