Chiral α-tertiary hydroxyaldehydes are very versatile building blocks in synthetic chemistry. Herein, we reported the first examples of a catalytic asymmetric protocol for the synthesis of such compounds from readily available α-halo or α-hydroxy ketones or enol silyl ethers with excellent yields and enantioselectivity. Its synthetic utility is demonstrated in the short, efficient formal synthesis of (S)-oxybutynin. In this process, the chiral ligand controls with the regioselectivity as well as enantioselectivity.