A facile strategy for synthesis of alpha-heterobifunctional polystyrenes is reported. The novel functional polystyrenes have been successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and chemical modification of end-functional groups. First, epsilon-caprolactone end-capped polystyrenes with controlled molecular weight and low polydispersity were prepared by ATRP of styrene using alpha-bromo-epsilon-caprolactone (alpha BrCL) as an initiator. Then, removal of the terminal bromine atom was performed with iso-propylbenzene in the presence of CuBr/PMDETA. Finally, ring-opening modifications of the caprolactone group were carried out with amines, n-butanol and H2O to produce novel polystyrenes containing two different functional groups at one end.