Poly(n-hexadecyl methacrylate) (PHMA) with narrow molecular weight distribution has been synthesized by atom transfer radical polymerization (ATRP) and reverse ATRP of n-hexadecyl methacrylate (HMA) at 80 A degrees C in N, N-dimethylformamide (DMF) using the CBr4/tris(2,2'-bipyridine)iron(III) complex initiation system in the presence of 2,2'-azobisisobutyronitrile (AIBN). From the kinetic studies and molecular weight data, it reveals the controlled nature of polymerization. The effect of various reaction parameters on number-average molecular weight (M (n) ) and molecular weight distribution (M (w) /M (n) ) have been investigated. For the reverse ATRP, the catalyst tris(2,2'-bipyridine)iron(III)complex, [Fe(bpy)(3)](3+), played an important role in polymerization rate and M (w) /M (n) . The resulting PHMA that obtained by reverse ATRP shows the best control of molecular weights and its distribution as compared to normal ATRP system. PHMA has been characterized by different techniques such as GPC, XRD and NMR spectroscopy.