The first highly enantioselective asymmetric decarboxylative addition of β-keto acids with 3-alkenyl-oxindoles bearing an all-carbon quaternary stereocenter have been developed. The relevant products were acquired in 49-98% yields with 88-98% enantioselectivities in the presence of 0.04-1.0 mol % of chiral rhodium catalyst. The comprehensive practicability of this method was proven in the preparation of the key intermediate, which can be easily transformed into analogues of physovenine and physostigmine.