Reverse atom transfer radical polymerization (ATRP) of styrene initiated with tetraethylthiuram disulfide (TD)/cuprous bromide (CuBr)/ 2,2'-bipyridine (bpy) has been successfully carried out at 120 C. The kinetic plot was first order in monomer. The measured number-average molecular weight was in good accordance with the theoretical one. Radical scavenger 1,1-diphenyt-2-picrylhydrazyl (DPPH) immediately terminated the reaction, which supported the radical essence of this polymerization. H-1 NMR and UV spectra analyses revealed alpha-S2CNEt2 and omega-Br end groups on the polystyrene chain. Conventional ATRP of methyl methacrylate could progress with the obtained polymer acting as the macroinitiator and CuBr/bpy or CuCl/bpy as the catalyst.