AbstractA highly efficient atom‐economic method for the preparation of chiral 3,3′‐bis(indolyl)methanes (3,3′‐BIMs) was developed. A chiral phosphoric acid (1 mol %) was found to promote the formation of structurally divers BIMs with quaternary stereogenic carbon centers in excellent yields with excellent enantioselectivities. Control experiments indicated that the simultaneous formation of two hydrogen bonds between the catalyst and the substrate was the key factor to obtain a good stereoselective outcome.