AFAIK, all ethanol production is via yeast or other fermentation microorganisms. Most of these use some sort of sugar as a substrate, but as janivar mentioned, efforts to generate ethanol from cellulose has recently been demonstrated.
In terms of other options, you could generate it using purified enzymes, but it would be difficult - you'd need about 1 dozen separate enzymes, electron carriers like NADP, energy source (ATP) and a range of substrates (ADP, phosphate, etc).
Synthetic ethanol is also made, largely for industrial uses, via the addition of water to ethane. According to wikipedia, only one company still does this; fermentable sugars being readily available and cheap these days.
Bryan