Alkoxy radicals have emerged as versatile intermediates to synthesis various organic molecules, and the development of convenient methods for their generation is highly desired. In this work, a new method for the facile access to alkoxy radicals from bench-stable N-alkoxyphthalimides promoted by Zn has been developed for the first time. These alkoxyl radicals subsequently undergo β-scission or hydrogen atom transfer to produce diverse and valuable alkyl radical species, which can be further trapped by α-trifluoromethyl alkenes to construct structurally diverse gem-difluoroalkenes in good yields.