This study reports the development of a porous coordination polymer (PCP) material that efficiently separates propylene (C3H8) from propane (C3H8) mixtures at 300 K through diffusion-rate sieving. The PCP material, named FDC-4, is designed with a cooperatively dynamic structure that combines global and local dynamics to control the adsorption processes. The global dynamics involve gate opening for C3H8 adsorption, while the local dynamics regulate the diffusion of C3H8. This design allows for significant differences in both adsorption capacity and kinetics, achieving a separation factor of 318, a C3H8 purity of 99.7%, and a C3H8 productivity of 19.5 L kg−1 in a single adsorption-desorption cycle. The material's performance is superior to existing methods, including energy-intensive cryogenic distillation, and demonstrates the potential for practical applications in petrochemical processes. The study also includes detailed synthesis, characterization, and kinetic studies to understand the underlying mechanisms of the separation process.This study reports the development of a porous coordination polymer (PCP) material that efficiently separates propylene (C3H8) from propane (C3H8) mixtures at 300 K through diffusion-rate sieving. The PCP material, named FDC-4, is designed with a cooperatively dynamic structure that combines global and local dynamics to control the adsorption processes. The global dynamics involve gate opening for C3H8 adsorption, while the local dynamics regulate the diffusion of C3H8. This design allows for significant differences in both adsorption capacity and kinetics, achieving a separation factor of 318, a C3H8 purity of 99.7%, and a C3H8 productivity of 19.5 L kg−1 in a single adsorption-desorption cycle. The material's performance is superior to existing methods, including energy-intensive cryogenic distillation, and demonstrates the potential for practical applications in petrochemical processes. The study also includes detailed synthesis, characterization, and kinetic studies to understand the underlying mechanisms of the separation process.