The atom transfer radical polymerization (ATRP) of styrene (St) was carried out in the presence of varying equivalents (eq) of hexafluorobenzene (HFB) to probe the effect of pi-pi stacking on the rate of the polymerization and the resulting tacticity of polystyrene (PSt) formed. The extent of interaction between the electron deficient face of the HFB and the electron rich face of the styrenic or polystyrenic phenyl ring was also examined as a function of reaction solvent, incorporating both non-aromatics (hexanes and THF) and aromatics (benzene and toluene). It was found that in all cases the rate of the ATRP of St was slowed by the addition of HFB to the reaction mixture, with increasing amounts of HFB (1 full eq. compared to St) retarding the rate to a relatively greater extent compared to smaller amounts (0.5 eq). Additionally, when aromatic solvents were used instead of hydrocarbons the effect of HFB on the rate of the ATRP was minimized, consistent with the solvent itself competing with the styrenic phenyl groups for pi pi stacking interactions with HFB. The decreased rate in the presence of HFB is consistent with a reduced ability of the terminal phenyl group on the PSt chain to stabilize the active polymer radical, pushing the equilibrium further to the dormant alkyl halide. This interaction between the dormant alkyl bromide and HFB was verified by H-1 NMR, with 1-bromoethylbenzene used as the alkyl bromide. When the ATRP of non-aromatic vinyl monomers was studied (butyl acrylate and methyl methacrylate), the effect of HFB on the system was almost unnoticeable as expected due to their inability to participate in pi-pi stacking interactions. The tacticity of the PSt formed in the presence of HFB was compared to PSt formed in its absence by observing the C1 resonance on C-13 NMR, but no change in the shape or chemical shift of the signal was observed. (C) 2010 Elsevier Ltd. All rights reserved.