Reactions of super-electron-donors (SEDs) derived from 4-dimethylaminopyridine and from N-methylbenzimidazole with α-methoxy-γ-alkoxyalkyl iodides lead to liberation of the γ-alkoxy groups as their alcohols. This is consistent with generation of alkyl radicals from the alkyl halide precursors, and trapping of these radicals by the radical-cation of the SED, followed by a heterolytic fragmentation.