We report radical coupling copolymerization (RCCP) of various pairs of in-situ formed benzyl-type biradicals derived from dibromides in the presence of Cu/ligand. The monomer sequence distributions and compositions of copolymers were measured by H-1 NMR. RCCP can be employed to synthesize some new kinds of polymers, such as polyether, polysulfone and poly(substituted arylene), under mild condition and within a short time. Copolymers with higher molecular weights than the corresponding homo-polymers prepared by radical coupling polymerization can be obtained by some pairs of monomers. (C) 2016 Elsevier Ltd. All rights reserved.