We report an iodine‐catalyzed Povarov reaction using indole as dienophile carried out in toluene at room temperature. This three‐component reaction, coupling an aldehyde, an amine, and an indole, proved to be an efficient method for synthesizing exo‐indolo[3,2‐c]quinoline derivatives related to the alkaloid isocryptolepine (cryptosanguinolentine) in good yield and with high stereoselectivity.