The catalytic direct dehydrative coupling of an alkene with an alcohol is one of the most straightforward and green strategies for the formation of Csp2−Csp2 bonds. However, previously reported studies have only dealt with achiral reactions. Here, we describe chiral Brønsted acid‐catalyzed direct catalyticasymmetric dehydrative coupling reactions of 3‐vinylindoles and 3‐indolylmethanols. Various structurally