A highly enantioselective organocatalytic Friedel–Crafts reaction of indoles with cyclic N-sulfimines using a chiral phosphoric acid as an organocatalyst has been developed. This organocatalytic reaction provides for the first time 3-indolyl sulfamidate derivatives in good yields and with high enantioselectivities (up to 97% ee) with a broad range of functional groups and substitution patterns.