Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique structures were synthesized for the first time. An X-ray single crystal structure analysis revealed that the two compounds are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed significant thermal stability and their structures remained stable up to 325 °C. The reaction conditions, type of substrate, amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy2M2L4 (OAc)2 (MeOH)5 (H2O)]) (M = Zn, Cd) exhibited excellent catalytic activity in the cycloaddition of CO2 and styrene oxide (C8H8O, SO). High product yields, high selectivity, and the highest turnover frequency (TOF) of 28 400 h-1 were achieved. Additionally, the catalysts can significantly enhance the application of the present types of 3d/4d-4f catalysts in catalysis for transformations involving the fixation of CO2.