A chiral bis(imidazolidine)pyridine (PyBidine)–Ni(OTf)2 complex smoothly catalyzed an asymmetric Friedel–Crafts reaction of 2-vinylindoles with nitroalkenes to give chiral indoles in a highly enantioselective manner while maintaining the 2-vinyl functionality. The chiral 2-vinylindoles offer unique chiral scaffolds for diverse transformations.