The iron(III)-catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully employed using tributylphosphine (TBP) and trimethylphosphite (TMP) as ligands in the absence of a reducing agent. The effects of solvent and initiator on polymerization of MMA were investigated. most of the polymerizations with these ligands were well controlled with a linear increase in the number average molecular weights ((M) over bar (n)) versus conversion and relatively low molecular weight distribution ((M) over bar (w)/(M) over bar (n) = 1.2-1.4) throughout the reactions, and the measured weights matched with the predicted values. The ethyl 2-bromoisobutyrate (EBriB) initiated ATRP of MMA with the FeBr3/TBP or FeBr3/TMP catalytic system was better controlled in toluene than in the other solvents used in this study at 80 degrees C.