A three-component carboetherification of unactivated alkenes has been developed allowing the rapid building of complexity from simple starting materials. A wide range of a-substituted styrenes underwent smooth reactions with unactivated alkyl nitriles and alcohols to afford g-alkoxy alkyl nitriles with concomitant generation of a quaternary carbon center. A radical clock experiment provided clear-cut evidence that the reaction proceeds through a tertiary alkyl radical intermediate.