Well-defined poly(n-docosyl acrylate) (PDA) with narrow molecular weight distribution has been synthesized by atom transfer radical polymerization (ATRP) and reverse ATRP of n-docosyl acrylate (DA) at 80 A degrees C in N,N-dimethylformamide using the carbon tetrabromide/FeCl3/2,2'-bipyridine (bpy) initiation system in the presence of 2,2'-azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO) as the source of reducing agent. The rates of polymerization for both the systems exhibit first-order kinetics with respect to the monomer, however, peroxide-initiated system shows slow rate of polymerization as compared to the azo-system. The effect of various reaction parameters on number average molecular weight (M (n) ) and molecular weight distribution (M (w)/M (n) ) have been investigated. The resulting PDA that obtained in presence of AIBN and BPO systems has been compared for both the conventional and reverse ATRP. The reverse ATRP initiated by peroxides behaves differently than that of the azo initiators. In reverse ATRP with BPO, the rate of polymerization (R (p)) has been significantly increased with the increase of BPO resulting higher M (n) and broader M (w)/M (n) . The reverse ATRP of DA did not exhibit living characteristics with BPO system. PDA has been characterized by GPC, FTIR, and NMR spectroscopy.