A simple and efficient approach to enantioenriched α,β-disubstituted γ-butyrolactones has been developed through multifunctional modular organocatalysis in a highly enantioselective (>99% ee) and diastereoselective (>30:1) manner following a one-pot sequential Michael-hemiacetalization-oxidation reaction. The catalytic process has great substrate compatibility, and the products have been transformed to synthetically useful molecules. The methodology has also been applied to the formal synthesis of (+)-Pilocarpine. © Copyright © 2019 American Chemical Society.