An efficient enantioselective alkylation of N‐unprotected 3‐substitutedoxindoles was realized by using a chiral N,N′‐dioxide/scandium(III) complex as the catalyst. A wide range of 3,3‐dialkyl substitutedoxindoles with quaternary stereocenters were obtained in high yields and ee values (up to 98% yield and 99% ee).