[en] PROBLEM TO BE SOLVED: To provide a method for synthesizing an alkoxyamine, and to provide a method for using the same in controlled radical polymerization. ; SOLUTION: This method for synthesizing the alkoxyamine expressed by general formula (I) or (II) [preferably, general formula (I)] comprises a one-pot process, wherein the process includes (1) reacting an oxidizing agent (A) with a sterically hindered secondary amine of general formula (III) in a water-containing medium to form a reaction product and an aqueous phase, (2) removing the aqueous phase, and (3) adding a free radical initiator (B) to the reaction product under such a condition that decomposition of the initiator is promoted to generate free radicals. Further, a method for polymerizing a monomer, namely the method for using the alkoxyamine synthesized by the method with originality, is provided