An asymmetric synthesis of silicon-stereogenic monohydrosilanes by rhodium-catalyzed dehydrogenative C-H silylation is developed. The process is suitable for the synthesis of various asymmetrically trisubstituted 1H-benzosiloles and 1H-benzosilolometallocenes in good yields with excellent chemo-, regio-, and stereocontrol. These selected silicon-stereogenic 1H-benzosilole compounds exhibit bright blue fluorescence and CPL (circular polarized luminescence) signals, which could be attractive to practitioners of materials science.