Iron-catalyzed alkylative cyclization of alkenes bearing oxygen nucleophiles with secondary and tertiary alkyl bromides through carbon-carbon and carbon-oxygen bond formations has been developed. A broad substrate scope is an attractive feature of this synthetic method, providing a variety of potentially bioactive five- and six-membered oxygen-containing heterocycles. The reaction pathway is proposed to involve a radical addition of the in situ-formed alkyl radical to an alkene followed by carbon-oxygen bond-forming intramolecular cyclization.