Bring a large pot of water to a boil. While that is heating, fill a large bowl full of ice water (this will be used as an ice bath).
With a sharp knife, cut a small X in the bottom of each peach. When the water comes to a boil, carefully place the peaches into the water and cook for 1 minute. (Cooking for much longer than 1 minute will make the peaches very soft to handle, so be sure to time this step. No need to bring the water back to a boil before you start timing the minute.)
With a slotted spoon, transfer the peaches to the ice water bath and let cool slightly.
Once the peaches have cooled, peel and pit the peaches and cut into 3/4-inch thick wedges. (If you aren't able to get the pit out easily - like me - try cutting the wedges all around the peach while the pit is still intact, and then used a knife to pry each wedge off the pit.)
Cut the vanilla bean in half the long way and with the tip of a knife, scrape out all of the seeds. In a medium pot, place the vanilla seeds and pod in with the two cups of water and the sugar. Bring to a boil, stirring so that the sugar completely dissolves.
Add the peaches and bourbon and simmer for about 5-7 minutes or until the peaches are tender but still hold their shape.
Transfer peaches to a bowl using a slotted spoon. Continue to cook the syrup over medium heat until reduced by half, about 15-20 minutes. Pour the syrup over the peaches and let cool completely.
Store peaches in a covered container in the refrigerator for up to a month - but I predict they won't last that long!
These peaches may also be canned and stored at room temperature for up to three months.