Provided is a method of living radical polymerization which does not necessitate complicated and intricate synthesis of a dormant species and which is highly efficient. A halogenated derivative compound is used as a dormant species for initiating living radical polymerization. The derivative compound is obtained by halogenating an alcohol compound having a non-conjugated structure or an amine compound having a non-conjugated structure with a halogenating agent capable of halogenating an alcohol or amine. A radical produced by elimination of halogen from the halogenated derivative compound is allowed to react with the unsaturated bond of the monomer. Thus, the monomer, which has a radical-reactive unsaturated bond, is polymerized by living radical polymerization. Preferably, the halogenating agent is a compound (NIS or the like) which also has a function as a catalyst.