A series of bicyclic polystyrenes were prepared by combining atom transfer radical polymerization and click coupling reaction. To investigate effect of experimental parameters, bicyclic polymers were prepared by changing types of ligands for click chemistry, concentration of polymers and coupling agents, feed rate of polymers and coupling agents, concentration of catalyst, and types of coupling agents. Purities of bicyclic polymers were estimated from SEC traces by Gaussian multiple peak fitting and subsequent peak integration. The purity of bicyclic polystyrene was achieved up to 78% when the reaction was conducted using CuBr/PMDETA catalyst and coupling agent having electron withdrawing group in diluted condition by slow addition of precursor polymer and coupling agent. (C) 2015 Elsevier Ltd. All rights reserved.