||Multicyclic polymers having complex cyclic structures have been expected to give new insight into the understanding physical properties based on their structures. However, their structure-property correlation study has been limited due to difficulty in their preparation with high purity. Therefore, there remains substantial interest in the preparation of topologically complex cyclic polymers with high purity. In this study, a series of bicyclic polystyrenes were prepared by combining atom transfer radical polymerization and “click” chemistry and by changing experimental parameters for cyclization. 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.