With the rapid advancements in asymmetric catalysis, there is a growing need for the asymmetric selective synthesis of complex and diverse molecules with chiral axes. Axially chiral molecules are not only present in natural products and drugs but also in specialized chiral ligands and catalysts. The catalytic asymmetric synthesis of axially chiral molecules has garnered significant attention within the chemical community. To date, two asymmetric catalytic methods have been established for the synthesis of biaxially chiral molecules: transition-metal catalysis and asymmetric organocatalysis. This feature article presents a summary of the research progress made in the field of asymmetric selective synthesis of biaxially chiral molecules. This review focuses on the reaction range, limitations, and reaction mechanism of the biaxially chiral molecular synthesis method, as well as the contribution and advantages of this method in the preparation of various axially chiral compounds.