Nitroxide-mediated free radical polymerizations (NMP) of styrene (St) and methyl methacrylate (MMA) were carried out in a room temperature ionic liquid: 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6). A bimolecular initiation system, benzoyl peroxide (BPO) along with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and a unimolecular initiation system, 2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane (alpha-hydrido alkoxyamine, TMPPAH)) were employed. Contrary to the results obtained for atom transfer radical polymerization (ATRP) and reversible addition-fragmentation radical transfer polymerization (RAFT) in the same ionic liquid, the molecular weights obtained in NMP were lower with broader polydispersities for a wide range of initiator ratios and temperatures due to the nonliving nature of polymerization.