The substituent redistribution of hydrosilanes on silicon through CSi and SiH bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective CSi/SiH bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(C6F5)(3). This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes.