The first deoxygenative hydrosilylation of ketones promoted by samarium diiodide and samarium has been reported. In this approach, secondary alkyl silanes are synthesized from unactivated ketones and chlorosilanes in one step. The carbonyl group of ketones is activated by SmI2-mediated single-electron transfer process, which follows a deoxygenative elimination of O=Sm. Broad substrate scope and excellent functional group tolerance has been demonstrated.