You make a great point. Obnoxious clarification - Ethanol evaporates about 5x faster than water. The exact details depend on the % of ethanol to water, and the distillation type.
Distillation will force most of the alcohol off first as only some of it is bound to the water, depending on the method and concentration before an azeotrope is found. The azeotrope is where the water and alcohol are bound and can't be further separated by distilling and boil off together. It's around 95% ethanol 5% water.