The separation of propane and propylene is the most energy-consuming and difficult separation process in the petrochemical industry because of their extremely similar physical properties. Separating propylene from propane using sorption can considerably reduce the energy consumed by current cryogenic distillation techniques. However, sorption involves several major challenges. An elastic layer-structured metal-organic framework (ELM-11) exhibited a highly efficient propane/propylene sorption separation, owing to its kinetic properties. Under equilibrium conditions, propane and propylene exhibited similar sorption capacities, gate opening pressures, and heats of sorption. Thus, their separation under equilibrium conditions is impractical. However, the sorption rates of the two gases were considerably different, showing different diffusion coefficients, resulting in a high kinetic selectivity (214 at 298 K) of propylene over propane on ELM-11. This kinetic selectivity is considerably higher than those obtained in previous studies. Thus, ELM-11 is a promising sorbent for separation technologies.