Preheat the oven to 350 degrees F.
In a medium saucepan, mix 1 cup water, 3/4 cup of the sugar, the butter and vanilla. Bring the sugar mixture to a boil over medium heat.
Peel and slice the peaches vertically into 10 slices each.
Separate each biscuit into 2 layers. Wrap a biscuit layer around a slice of peach, stretching the biscuit slightly to overlap, and seal on the bottom. Place the wrapped slices, sealed-side down, in a casserole dish. Pour the hot sugar mixture over the peach slices. Mix the remaining 1/4 cup sugar with the cinnamon and sprinkle the mixture over the tops of the wrapped peaches. Bake until golden brown, 40 minutes.