In recent advances in controlled radical polymerization, atom transfer radical polymerization (ATRP) has achieved increasing interest. This investigation reports the ATRP of methyl methacrylate (MMA) using pseudohalogens as initiator as well as an anion for copper catalyst. The results were compared with the conventional halide system. Different pseudohalides were used as the initiator for the ATRP of MMA in combination with CuX (X = pseudohalide or halide) as the catalyst. Pseudohalide initiator in combination with Cu(halide) catalyst leads to inefficient ATRP due to slow initiation. Pseudohalide initiator in combination with Cu(pseudohalide) catalyst leads to uncontrolled or no polymerization. The polymers were characterized by using GPC, IR, MALDI-TOF-MS, and TGA analysis. IR and MALDI analysis showed that the resultant polymer had pseudohalide as the end group. (c) 2006 Wiley Periodicals, Inc.