In this contribution, we for the first time propose the targeted synthesis of Co-metalated salen-based crystalline polymer, starting from corner and square building units in the presence of cobalt metal ions. On the basis of structural characterizations, this kind of salen-based crystalline polymer is proved to be the long hollow tube. Due to its covalent connected unique structure, the obtained Co-salen polymer possesses high crystallinity and excellent stability. The experimental and theoretical studies show that this kind of material holds paramagnetism, unique electronic structure, and remarkable catalytic activity with high selectivity for the coupling of CO2 and epoxides to form cyclic carbonates. And specifically, it shows favorable recyclability with only a slight drop in yield after six catalytic cycles. We hope that the results reported here will greatly inspire the design and synthesis of different metalated salen-based polymer and enlarge their interesting applications in the future. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 641-647