Periodic polymers with different repeating sequences, such as [AX], [AAX] and [ABAX], were synthesized by radical addition-coupling polymerization (RACP) of bifunctional monomers with benzyl bromide/alpha-methyl benzyl bromide groups and 2-methyl-2-nitrosopropane in the presence of Cu(0)/ligand. By selection of proper ligand and polymerization condition, the defects derived from self-coupling of benzyl-type radicals were eliminated, which results in strict control on the repeating sequence. (C) 2016 Elsevier Ltd. All rights reserved.