Comprehensive SummaryP,N‐Atropisomers are valuable structural motifs, widely utilized as chiral ligands and in various catalytic systems. However, the asymmetric synthesis of these compounds from readily available starting materials remains a significant challenge. In this study, we present a chiral phosphoric acid‐catalyzed atroposelective synthesis of axially chiral aminophosphines via dynamic kinetic resolution. This approach effectively addresses the aforementioned challenge through featuring the use of readily available starting materials, mild reaction conditions, high yields, excellent enantioselectivities, and a broad substrate scope, underscoring its practicality and synthetic utility.