AbstractFor more than five decades, P‐stereogenic aminophosphine chalcogenides and boranes have attracted scientific attention and are still in the focus of ongoing research. In the last years, novel transition metal‐based synthesis methods have been discovered, in addition to the long‐known use of chiral auxiliaries. Enantiomerically pure compounds with N−P⁺−X⁻ (X=O, S, BH₃) motifs served as valuable reactive building blocks to provide new classes of organophosphorus derivatives, thereby preserving the stereochemical information at the phosphorus atom. Over the years, intriguing applications in organocatalysis and transition metal catalysis have been reported for some representatives. Asymmetric reductions of C=C, C=N, and C=O double bonds were feasible with selected P‐stereogenic aminophosphine oxides in the presence of hydrogen transfer reagents. P‐stereogenic aminophosphine boranes could be easily deprotected and used as ligands for various transition metals to enable catalytic asymmetric hydrogenations of olefins and imines. This review traces the emergence of a synthetically and catalytically powerful functional compound class with phosphorus‐centered chirality in its main lines, starting from classical approaches to modern synthesis methods to current applications.