The development of a straightforward strategy to obtain enantioenriched silicon‐stereogenic benzosiloles remains a challenging yet appealing synthesis venture due to their potential future application in chiral electronic and optoelectronic devices. In this context, all of the existing methods rely on Rh‐catalyzed systems and are somewhat limited in scope. Herein, we disclose the first Ni0‐catalyzed ring expansion process that enables the preparation of benzosiloles possessing tetraorganosilicon stereocenters in excellent yields and enantioselectivities. The presented catalysis strategy is further applied to the asymmetric synthesis of silicon‐stereogenic bis‐silicon‐bridged π‐extended systems. Preliminary studies reveal that such compounds exhibit fluorescence emission, Cotton effects and circularly polarized luminescence (CPL) activity. We disclosed a state‐of‐the‐art strategy for the asymmetric synthesis of enantioenriched silicon‐stereogenic benzosiloles in excellent yields and enantioselectivities enabled by a Ni0/chiral PR3‐catalyst system. Moreover, preliminary studies on the chiroptical properties of silicon‐stereogenic bis‐silicon‐bridged π‐extended systems, which were synthesized by the presented catalysis strategy, are also described.