The ＂living＇/controlled radical polymerization （LRP） of styrene （St） at room temperature is rarely reported. In this work, copper（0） （Cu（0））-mediated radical polymerization of St at room temperature was investigated in detail. Dimethyl sulfoxide （DMSO）, N,N-dimethylformamide （DMF） as well as a binary solvent, tetrahydrofuravdl,l,l,3,3,3-hexafluoro-2- propanol were used as the solvents, respectively. Methyl-2-bromopropionate and ethyl 2-bromoisobutyrate were used as the initiators, respectively. The polymerization proceeded smoothly with moderate conversions at room temperature. It was found that DMF was a good solvent with the essential features of LRP, while DMSO was a poor solvent with uncontrollable molecular weights. Besides, the match among the initiator, solvent and molar ratios of reactants can modulate the livingness of the polymerization, and the proper selection of ligand was also crucial to a controlled process. This work provided a first example of Cu（0）-mediated radical polymerization of St at room temperature, which would enrich and strength the LRP technique.
