Place 1 peach in boiling water, and cook for 30 seconds to 1-1/2 minutes.*
Using slotted spoon, transfer peach to ice water.
Repeat with remaining peaches.
Take peach out of ice water and remove skin.
After all peaches have been peeled, cut each peach into thin wedges.
Empty and dry the medium-sized bowl, and return sliced peaches to it.
Combine sugar and water in a small pot over high heat, stirring until sugar dissolves.
Add bourbon and vanilla.
Pour prepared bourbon mixture over peaches.
Allow to poach and cool for at least 30 minutes.
Cover, transfer to refrigerator, and chill for 12 hours or overnight.
Serve as desired.
A few serving ideas: as is, atop vanilla ice cream or pound cake
Notes
The boiling time for the peaches will vary, depending on how ripe they are. Very ripe peaches need 30 seconds. Less ripe peaches could need 1 to 1-1/2 minutes.