In a small saucepan, gently simmer sugar and water until sugar dissolves. Remove from heat and set aside.

Remove stems and seeds from chile pods. Toast chiles in a pan over medium heat until they are fragrant, about 5 minutes. Cut vanilla bean into pieces that are about 2–3 inches in length. In a blender, combine chiles, simple syrup, and vanilla bean. Strain through a cheesecloth. Store in refrigerator for up to 2 weeks.