A combination of ring-opening metathesis polymerization (ROMP) and click chemistry approach was utilized for the first rime in preparation of multiblock copolymers The dibromo-functionalized telechelic poly(butadiene) (PBD) was synthesized firstly by ROMP of 1,5-cyclooctadiene in the presence of a symmetrical difunctional chain transfer agent and transformed into diazido-telechelic PBD, which was then reacted with a dialkynyl-containing azobenzene chromophore via click reaction, producing novel multiblock PBDs collected by azobenzene groups and newly formed triazole moieties The monomer and polymer were characterized by IR. UV-vis, LC/MS, and NMR techniques. The produced multiblock copolymers have molecular weights within 13.3 and 578 kDa, and their polydispersity indices ranging from 1 98 to 238 by gel permeation chromatography measurement The multiblock PBDs containing azo chromophores and triazole moieties with or without hydrogen-bonding interreaction with 4,4'-dihydroxybiphenyl molecule exhibited different photoisomerization efficiency from trans to cis as observation in UV-vis spectroscopy The morphologies of multiblock PBDs were also investigated by atom force microscopy. (C) 2010 Elsevier Ltd All rights reserved.