Bring a large pot of water to a boil. Meanwhile, prepare an ice-water bath. Cut a small X into the bottom of each peach. Boil peaches for 1 minute.
Transfer to ice-water bath. Let cool slightly. Peel and pit peaches, and cut into 3/4-inch-thick wedges.
Bring 4 cups water, the sugar, and vanilla seeds and pods to a boil in a large saucepan, stirring until sugar dissolves. Add peaches and bourbon. Simmer until peaches are tender but still hold their shape, 5 to 7 minutes.
Transfer peaches to a large bowl using a slotted spoon. Cook syrup over medium
heat until reduced by half, about 15 minutes. Pour over peaches. Let cool completely.
Divide peaches among five 12-ounce sterilized jars using a slotted spoon. (Jars can be sterilized by boiling in water, submerged, for 10 minutes.) Pour syrup over tops. Add vanilla pods to jars if desired. Seal jars, and refrigerate until ready to use.
Peaches can be refrigerated for up to 1 month. Canned peaches can be stored at room temperature for up to 3 months. For canning instructions, visit wholeliving.com/photogallery/canning-recipes-and-tips.