The treatment of a variety of hydrosilanes, each incorporating a benzylic C (sp3)–H bond, with a rhodium catalyst resulted in intramolecular dehydrogenative silylation. This silylation reaction was found to occur at typically unreactive C (sp3)–H bonds located at terminal positions on alkyl chains. Interestingly, the rhodium catalyst also promoted regioselective silylation at a site internal to an alkyl chain.