Make the vanilla syrup: In a medium saucepan set over medium-high heat, combine the sugar and 1 cup water and cook until the sugar dissolves. Transfer to a lidded container and add the vanilla pod and seeds. Cover and let sit overnight. Discard the vanilla pod.
Make the cinnamon syrup: In a medium saucepan set over medium-high heat, combine the sugar and 1 cup water and cook until the sugar dissolves. Transfer to a lidded contained and add the cinnamon bark. Cover and let sit overnight. Discard the cinnamon.
Make the cocktail: Fill a mixing glass with ice. Add the bitters, Campari, vanilla syrup, cinnamon syrup, rye and bourbon and stir until chilled. Strain into a rocks glass filled with the large ice cube and garnish with the orange peel.