Straightforward C-H silylation of heteroarenes and alkenes was found to provide efficient access to organo-HOMSi reagents as stable silicon reagents for cross-coupling. Various heteroarenes and terminal alkenes were silylated to show the versatility of the reaction. This method was applied in double silylation reactions to give bisHOMSi reagents. The silylation products could be used in the cross-coupling reaction with haloarenes easily.