Abstract Asymmetric catalysis is one of the most attractive and efficient ways of synthesizing chiral enantioenriched compounds from achiral precursors. Compared with the well‐investigated enantioselective preparation of carbon‐stereogenic compounds, the corresponding preparation of silicon‐stereogenic compounds is much less established. In particular, the available methods typically rely on the use of stoichiometric amounts of chiral reagents, and little progress has been made on catalytic enantioselective synthesis using prochiral organosilanes until recently. This Focus Review highlights recent advances in the catalytic enantioselective preparation of silicon‐stereogenic organosilanes under transition‐metal catalysis through desymmetrization of prochiral organosilanes including diorganodihydrosilanes and tetraorganosilanes.