A new dual palladium/scandium catalysis starting from β-alkynyl ketones and o-alkynyl anilines is reported for the first time,leading to the atom-economic synthesis of rotationally hindered C3-naphthylated indoles in moderate to good yields and high regioselectivi-ty.This method can tolerate normal air conditions,and features the use of palladium/scandium cooperative catalysts without any ligand,facile double annulation involving various internal alkynes,and good functional group tolerance.