Sn(0)-mediated single electron transfer-living radical polymerization (SET-LRP) of acrylonitrile (AN) with carbon tetrachloride (CCl4) as initiator and hexamethylenetetramine (HMTA) as ligand in N, N-dimethylformamide (DMF) was studied. The polymerization obeyed first order kinetic. The molecular weight of polyacrylonitrile (PAN) increased linearly with monomer conversion and PAN exhibited narrow molecular weight distributions. Increasing the content of Sn(0) resulted in an increase in the molecular weight and the molecular weight distribution. Effects of ligand and initiator were also investigated. The block copolymer PAN-b-polymethyl methacrylate with molecular weight at 126,130 and polydispersity at 1.36 was successfully obtained. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012