The atom transfer radical polymerizations (ATRPs) of styrene initiated by diselenocarbamates were carried out for the first time. The polymerization showed first-order kinetic with respect to the monomer concentration, and the molecular weights of the obtained polymers increased linearly with the monomer conversions with narrow molecular weight distributions (as low as 1.16). The results of chain extension, H-1 NMR, UV-vis, and MALDI-TOF MS confirmed that the resultant polystyrene possessed some degree of living diselenocarbamates terminal. However, significant amounts of dead polymers (about 53%) were also found. This work offered an alternative type of ATRP initiator, and the seleno-terminated polymers may be useful in biotechnological and biomedical applications. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1927-1933