<p>Chiral α,β,β-triaryl tertiary alcohols represent significant structural motifs that find extensive applications in pharmaceuticals and bioactive molecules. Their distinctiveness lies in their unique three-dimensional architectures, which are conducive to interactions with biological targets, thus making them particularly worthy of attention. However, the stereocontrolled assembly of adjacent chiral centers within these sterically congested scaffolds has remained a formidable challenge. Herein, we present a Cu-catalyzed dynamic kinetic asymmetric allylation of racemic α,β,β-triarylethanones, providing efficient access to a diverse range of chiral α,β,β-triaryl tertiary alcohols with robust enantioselectivity and diastereoselectivity. When combined with subsequent transformations, this method establishes a highly flexible platform for the synthesis of antitubercular agent (<i>S,S</i>)-TBAJ-587 and bedaquiline stereoisomers. Mechanistic investigations, including control experiments, density functional theory calculations, and interaction region indicator analyses, indicate that the steric characteristics of the ligand and weak intermolecular interactions synergistically lower the reaction energy barrier and enhance both reaction activity and stereocontrol.</p>