Atom transfer radical polymerization of stearyl methacrylate (SMA) was successfully carried out in N,N-dimethylformamide using the carbon tetrabromide/Fe(III)/2,2'-bipyridine initiator system in the presence of 2,2'-azobisisobutyronitrile (AIBN) as the source of the reducing agent to maintain the equilibrium between growing radicals and dormant species. The molecular weights of the resulting poly(stearyl methacrylate) (PSMA) increased with the conversion and the molecular weight distribution of PSMA was quite narrow. The rates of polymerization exhibit first-order kinetics with respect to the monomer. A probable reaction mechanism for the polymerization system was postulated to explain the observed results.