Bring pot of water to rolling boil; plunge peaches into water until skins loosen, about 30 seconds. Drain and chill in ice water. Halve peaches; remove pits and slip off skins.

Meanwhile, in large saucepan, bring 3 cups (750 mL) water, wine, sugar, lemon rind and vanilla bean to simmer, stirring occasionally, over medium heat. Add peaches and return to boil. Remove from heat; let cool completely. Using slotted spoon, transfer peaches to bowl. Set aside.

Meanwhile, remove rind from syrup; return to boil over medium-high heat. Boil until reduced to 3/4 cup (175 mL), about 30 minutes. Let cool. Scrape seeds from vanilla bean into syrup and return bean to syrup. Pour syrup over peaches; cover and refrigerate until cold, about 1 hour. (Make-ahead: Refrigerate for up to 2 days.) For each serving, drizzle two peach halves with 1 tbsp (15 mL) of the syrup.

Makes 4 servings.