The living polymerization of N,N-dimethylacrylamide was achieved by atom transfer radical polymerization catalyzed by copper chloride complexed with a new ligand, N,N'-bis(pyridin-2-ylmethyl 3-hexoxo-3-oxopropyl)ethane 1,2-diamine (BPED). With methyl 2-chloropropionate as the initiator, the polymerization reached high conversions (>90%) at 80degreesC and 100degreesC, producing polymers with (M) over bar (n) very close to theoretical values and low polydispersity. The ligand, temperature, and copper halide strongly affected the activity and control of the polymerization.