tert-Butoxy radical, generated by Ti (III)-one electron reduction of tert-butylhydroperoxide, selectively abstracts an α-H atom from ethers. The resulting α-ethereal radicals add to the C- atom of methylene iminium salts, formed in situ under aqueous acidic conditions, leading to a one-pot aminomethylation of ethers at room temperature. The aminoalkylation of ethers is also considered and the role of the metal ion is discussed.